CN111269417A - Pyridyl-containing conjugated microporous polymer and preparation method and application thereof - Google Patents

Pyridyl-containing conjugated microporous polymer and preparation method and application thereof Download PDF

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CN111269417A
CN111269417A CN201911170206.8A CN201911170206A CN111269417A CN 111269417 A CN111269417 A CN 111269417A CN 201911170206 A CN201911170206 A CN 201911170206A CN 111269417 A CN111269417 A CN 111269417A
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pyridyl
microporous polymer
conjugated microporous
aromatic
polymer
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CN111269417B (en
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廖耀祖
曾沁若
左宏瑜
闫春娜
朱桐桐
程中桦
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Zhenjiang Liedun Special Materials Co Ltd
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Abstract

The invention discloses a pyridyl-containing conjugated microporous polymer and a preparation method and application thereof, wherein the pyridyl-containing conjugated microporous polymer is synthesized by condensing and conjugating two carbonyl-containing aromatic compounds in a pyridine environment, cyclizing the two carbonyl-containing aromatic compounds with ammonia to form a pyridine ring, and doping pyridine nitrogen. The polymer has potential application value in the fields of gas adsorption and separation, energy storage, catalysis, electrochemistry and the like; the preparation method is simple and convenient to operate, and the prepared polymer has excellent rigidity, thermal stability and chemical stability, can be used in the fields of adsorption separation, energy storage, catalysis and electrochemistry, and has the advantages of wide application range, good adsorption effect, high adsorption capacity and low cost.

Description

Pyridyl-containing conjugated microporous polymer and preparation method and application thereof
Technical Field
The invention belongs to the field of synthesis of adsorption separation materials, and particularly relates to a pyridyl-containing conjugated microporous polymer, and a preparation method and application thereof.
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 resistance2The selectivity is poor, and the adsorption capacity needs to be improved; therefore, it is necessary to develop a material with low cost, high adsorptivity and low consumption to replace the existing material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a pyridyl-containing conjugated microporous polymer, a preparation method and application thereof.
In order to solve the technical problems, the invention provides a pyridyl-containing conjugated microporous polymer, which is synthesized by performing condensation and conjugate addition on two carbonyl-containing aromatic compounds in a pyridine environment and cyclizing the two carbonyl-containing aromatic compounds with ammonia to form a pyridine ring.
The technical scheme of the invention is further defined as follows:
furthermore, in the above pyridyl-containing conjugated microporous polymer, the aromatic compound is a mixture of an aromatic ketone compound and an aromatic aldehyde compound, and the aromatic ketone compound and the aromatic aldehyde compound in the aromatic compound are represented by the formula: ketone group =1:2 molar ratio.
In the pyridyl-containing conjugated microporous polymer, the aromatic ketone compound is 1, 4-diacetylbenzene or 1,3, 5-triacetylbenzene; the aromatic aldehyde compound is one of 1,3, 5-tri (p-formylphenyl) benzene, 2,4, 6-tri (4-formylphenyl) -1,3, 5-triazine and tri- (4-formylphenyl) amine.
The invention also designs a preparation method of the pyridyl-containing conjugated microporous polymer, which comprises the following specific preparation processes:
mixing two aromatic compounds, namely aromatic aldehyde compounds and aromatic ketone compounds, adding ammonium acetate and pyridine, placing the mixture in an oil bath kettle to react at a certain temperature and a certain rotating speed, and then filtering, washing and vacuum drying to obtain the target product, namely the pyridyl-containing conjugated microporous polymer.
The technical scheme of the invention is further defined as follows:
further, in the above method for preparing a pyridyl-containing conjugated microporous polymer, the molar ratio of ammonium acetate: aromatic =10: 1.
In the preparation method of the pyridyl-containing conjugated microporous polymer, the pyridyl-containing conjugated microporous polymer is placed in an oil bath pot and is heated and stirred at the temperature of 110-120 ℃ for reaction for 12-24 h.
In the preparation method of the pyridyl-containing conjugated microporous polymer, deionized water and an organic solvent are sequentially adopted for washing at 60-80 ℃ during washing, and the washing time is 24 hours.
In the preparation method of the pyridyl-containing conjugated microporous polymer, the organic solvent is at least one of DMSO, methanol, and chloroform.
In the preparation method of the pyridyl-containing conjugated microporous polymer, the technological parameters of vacuum drying are as follows: the vacuum drying temperature is 60-100 ℃, and the vacuum drying time is 20-24 h.
Preferably, the volume of pyridine added is 100-200 mL.
The invention also designs an application of the pyridyl-containing conjugated microporous polymer as a carbon dioxide adsorbent for adsorbing and separating carbon dioxide.
The invention has the beneficial effects that:
the invention adopts two aromatic compounds containing carbonyl groups as reaction monomers 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 polymer has potential application values in the fields of gas adsorption and separation, energy storage, catalysis, electrochemistry and the like.
Synthesized by the invention as CO2The pyridyl is introduced to provide selective adsorption, and the existence of the pyridine ring provides rigidity, thermal stability and chemical stability for the polymer and can be used as an affinity active site, so that the aim of adsorbing gas is fulfilled; the adsorption capacity is improved by changing the construction unit and optimizing the specific surface area and the pore structure; and the cost is low due to nonmetal coupling.
Drawings
FIG. 1 is an FTIR plot of pyridyl-containing conjugated microporous polymer-1 synthesized in example 1;
FIG. 2 shows the N at 77.4K of the pyridyl-containing conjugated microporous polymer 1 synthesized in example 12Adsorption-desorption curve of (a);
FIG. 3 is a schematic representation of the pyridine group-containing conjugated microporous polymer-2 synthesized in example 213C-NMR chart
FIG. 4 shows CO at 273K of the pyridyl-containing conjugated microporous polymer-2 synthesized in example 22Adsorption-desorption curves;
FIG. 5 shows the CO at 273K of the pyridine/bipyridine-containing conjugated microporous polymer 2 synthesized in example 22And N2Initial adsorption slope curve of (1);
FIG. 6 shows the N at 77.4K of the pyridyl-containing conjugated microporous polymer 3 synthesized in example 32Adsorption-desorption curve of (a);
FIG. 7 is the pyridyl-containing compound synthesized in example 3CO of conjugated microporous Polymer-3 at 298K2Adsorption-desorption curves;
FIG. 8 shows the CO at 298K of the pyridyl-containing conjugated microporous polymer-3 synthesized in example 32And N2Initial adsorption slope curve of (1);
FIG. 9 shows the N at 77.4K of the pyridyl-containing conjugated microporous polymer-4 synthesized in example 42Adsorption-desorption curve of (a);
FIG. 10 shows the CO at 298K of the pyridyl-containing conjugated microporous polymer-4 synthesized in example 42Adsorption-desorption curves;
FIG. 11 shows the CO at 298K of the pyridyl-containing conjugated microporous polymer-4 synthesized in example 42And N2Initial adsorption slope curve of (1);
FIG. 12 shows the N at 77.4K of the pyridyl-containing conjugated microporous polymer-5 synthesized in example 52Adsorption-desorption curve of (a);
FIG. 13 shows the CO at 298K of the pyridyl-containing conjugated microporous polymer-5 synthesized in example 52Adsorption-desorption curves;
FIG. 14 shows the CO at 298K of the pyridyl-containing conjugated microporous polymer-5 synthesized in example 52And 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.
Example 1
The preparation method of the pyridyl-containing conjugated microporous polymer provided by the embodiment is as follows: 1, 4-Diacetobenzene (243.3 mg, 1.5 mmol) and tris- (4-formylphenyl) amine (164.7 mg, 0.5 mmol) were combined and placed in a 200mL round-bottomed flask at ambient temperature and pressure, ammonium acetate (1.54 g, 20 mmol) was added, and 100mL pyridine was added to complete the mixtureAnd (3) completely dissolving the powder, and finally placing the mixed solution at the oil bath temperature of 115 ℃ to stir for reaction for 24 hours. After the reaction, carrying out suction filtration in a sand core funnel, stirring and washing the mixture for 24 hours at the temperature of 60 ℃ by using deionized water, methanol and chloroform respectively, carrying out 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, namely the polymer-1, wherein the BET specific surface area of the polymer-1 is 304m2/g。
The infrared spectrum of the polymer-1 obtained in this example is shown in fig. 1, and the peaks of two C = O of the reacted monomers at 1678 and 1667 are obviously weakened, which proves that the aldehyde group and ketone group of the two monomers are reacted, and a new peak of C = N appears at 1589, indicating that a pyridine ring is likely to be formed.
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)0=0.1 to 1.0), the curve rises at a relatively slow rate, indicating the presence of macropores in the 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.
Example 2
The preparation method of the pyridyl-containing conjugated microporous polymer provided by the embodiment is as follows: 1, 4-diacetylbenzene (243.3 mg, 1.5 mmol) and 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine (196.7 mg, 0.5 mmol) were mixed and placed in a 200ml round bottom flask at normal temperature and pressure, ammonium acetate (1.54 g, 20 mmol) was added, 100ml pyridine was then 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, the filtration is carried out in a sand core funnel, the filtration is respectively stirred and washed for 24 hours by deionized water (60 ℃), DMSO (80 ℃), methanol (60 ℃) and chloroform (60 ℃), the filtration is carried out, and then the filtration is carried out, the drying is carried out in a vacuum oven at 60 ℃ for 24 hours, and the conjugate micropore containing the pyridyl is obtainedPolymer, designated Polymer-2, had a BET specific surface area of 325m2/g。
Preparation of Polymer-2 obtained in this example13The results of the C-NMR measurement are shown in FIG. 3, 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 example2As shown in fig. 4, the adsorption and desorption curves show that the adsorption curve rapidly rises in the low pressure region, indicating that the microporous structure of the polymer has a certain effect on the adsorption of CO 2. CO of Polymer-2 at 273K, 1 Bar2The 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. 5, 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
The preparation method of the pyridyl-containing conjugated microporous polymer provided by the embodiment is as follows: 1,3, 5-triacetylbenzene (408.5 mg, 2 mmol) and 1,3, 5-tris (p-formylphenyl) benzene (390.4 mg, 1 mmol) were mixed and placed in a 200ml round-bottomed flask at normal temperature and pressure, ammonium acetate (2.31 g, 30 mmol) 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, carrying out suction filtration in a sand core funnel, respectively stirring and washing with deionized water, methanol and chloroform at 60 ℃ for 24h, placing in a vacuum oven at 60 ℃ after suction filtration for drying for 24h to obtain the pyridyl-containing conjugated microporous polymer,as the polymer-3, its BET specific surface area was 511m2/g。
Polymer 3 obtained in this example has an N value at 77.4K2As shown in FIG. 6, 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)0=0.1 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 example2As shown in fig. 7, it can be seen that the adsorption curve rapidly increases in the low-pressure region, indicating that the microporous structure of the polymer has a certain effect on the adsorption of CO 2. CO of Polymer-2 at 298K, 1 Bar2The 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. 8, 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
The preparation method of the pyridyl-containing conjugated microporous polymer provided by the embodiment is as follows: 1,3, 5-triacetylbenzene (408.5 mg, 2 mmol) and tris- (4-formylphenyl) amine (329.4 mg, 1 mmol) were mixed and placed in a 200ml round-bottomed flask at normal temperature and pressure, ammonium acetate (2.31 g, 30 mmol) 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, carrying out suction filtration in a sand core funnel respectivelyStirring and washing deionized water, methanol and chloroform at 60 ℃ for 24h, filtering, and drying in a vacuum oven at 60 ℃ for 24h to obtain the pyridyl-containing conjugated microporous polymer, marked as polymer-4, with the BET specific surface area of 523m2/g。
Polymer 4 obtained in this example has an N value of 77.4K2As shown in FIG. 9, 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)0=0.1 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 the polymer-3 and could not be completely desorbed.
CO at 298K for Polymer-4 obtained in this example2As shown in fig. 10, the adsorption/desorption curves show that the adsorption curve rapidly increases in the low-pressure region, indicating that the microporous structure of the polymer has a certain effect on the adsorption of CO 2. CO of Polymer-4 at 298K, 1 Bar2The 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 example had CO at 298K2And N2The initial adsorption slope curve of (A) is shown in FIG. 11, 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
The preparation method of the pyridyl-containing conjugated microporous polymer provided by the embodiment is as follows: 1,3, 5-triacetylbenzene (204.3 mg, 1 mmol), 2,4, 6-tris (4-formylphenyl) -1,3, 5-triazine (196.7 mg, 0.5 mmol) were mixed and placed in a 200ml round-bottom flask at normal temperature and pressure, ammonium acetate (1.15 g, 15 mmol) was added, and then 100ml of ammonium acetate was addedPyridine is used for dissolving all the mixed powder, and finally the mixed solution is placed at the oil bath temperature of 115 ℃ to be stirred and reacted for 24 hours. After the reaction is finished, performing suction filtration in a sand core funnel, stirring and washing for 24 hours in deionized water (60 ℃), DMSO (80 ℃), methanol (60 ℃), chloroform (60 ℃), performing suction filtration, and then drying for 24 hours in a vacuum oven at 60 ℃ to obtain the pyridyl-containing conjugated microporous polymer, namely the polymer-4, wherein the BET specific surface area of the pyridyl-containing conjugated microporous polymer is 515m2/g。
Polymer 5 obtained in this example has an N value at 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-5; in the middle and high relative pressure region (P/P)0=0.1 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-3 and could not be completely desorbed.
CO at 298K for Polymer-5 obtained in this example2As shown in fig. 13, the adsorption/desorption curves show that the adsorption curve rapidly increases in the low-pressure region, indicating that the microporous structure of the polymer has a certain effect on the adsorption of CO 2. CO of Polymer-5 at 298K, 1 Bar2The 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-4 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. 14, and the fitted CO is calculated2And N2The ratio of the initial adsorption curve slopes indicates the CO2/N2The adsorption selectivity is 47.0, and the adsorption selectivity is good.
Synthesized by the invention as CO2Process for preparing pyridyl-containing conjugated microporous polymers of adsorbents by introducing pyridyl groups to provide selective adsorption of the pyridine ringThe polymer has the advantages of providing rigidity, thermal stability and chemical stability for the polymer, and simultaneously serving as an active site for affinity, thereby achieving the purpose of adsorbing gas; the adsorption capacity is improved by changing the construction unit and optimizing the specific surface area and the pore structure; and the cost is low due to nonmetal coupling.
In addition to the above embodiments, the present invention may have other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.

Claims (10)

1. A pyridyl-containing conjugated microporous polymer characterized by: two kinds of carbonyl-containing aromatic compounds are subjected to condensation and conjugated addition in a pyridine environment, and are cyclized with ammonia to form a pyridine ring, so that the pyridine nitrogen-doped conjugated microporous polymer is synthesized.
2. The pyridyl-containing conjugated microporous polymer of claim 1, wherein: the aromatic compound is a mixture of an aromatic ketone compound and an aromatic aldehyde compound, wherein the aromatic ketone compound and the aromatic aldehyde compound in the aromatic compound are expressed by aldehyde group: ketone group =1:2 molar ratio.
3. The pyridyl-containing conjugated microporous polymer of claim 2, wherein: the aromatic ketone compound is 1, 4-diacetylbenzene or 1,3, 5-triacetylbenzene; the aromatic aldehyde compound is one of 1,3, 5-tri (p-formylphenyl) benzene, 2,4, 6-tri (4-formylphenyl) -1,3, 5-triazine and tri- (4-formylphenyl) amine.
4. The preparation method of the pyridyl-containing conjugated microporous polymer is characterized by comprising the following specific preparation processes of:
mixing two aromatic compounds, namely aromatic aldehyde compounds and aromatic ketone compounds, adding ammonium acetate and pyridine, placing the mixture in an oil bath kettle to react at a certain temperature and a certain rotating speed, and then filtering, washing and vacuum drying to obtain the target product, namely the pyridyl-containing conjugated microporous polymer.
5. The method of claim 4, wherein the molar ratio of ammonium acetate: aromatic =10: 1.
6. The method of claim 4, wherein the step of preparing the conjugated microporous polymer comprises: placing the mixture in an oil bath kettle to be heated and stirred at the temperature of 110-120 ℃ for reaction for 12-24 h.
7. The method of claim 4, wherein the step of preparing the conjugated microporous polymer comprises: the washing is carried out by sequentially adopting deionized water and an organic solvent at the temperature of 60-80 ℃ for 24 h.
8. The method of claim 7, wherein the step of preparing the conjugated microporous polymer comprises: the organic solvent is at least one of DMSO, methanol and chloroform.
9. The method of claim 4, wherein the step of preparing the conjugated microporous polymer comprises: the technological parameters of the vacuum drying are as follows: the vacuum drying temperature is 60-100 ℃, and the vacuum drying time is 20-24 h.
10. Use of the pyridyl-containing conjugated microporous polymer according to claim 1, wherein: the adsorbent is used for adsorbing and separating carbon dioxide.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111841509A (en) * 2020-07-08 2020-10-30 东华大学 High CO2Selective polymer adsorbent and preparation method thereof
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
CN114849778A (en) * 2021-02-04 2022-08-05 湖南大学 Silver-loaded catalyst of hydrophilic bipyridyl conjugated microporous polymer and preparation method and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109880087A (en) * 2019-03-13 2019-06-14 福州大学 A kind of covalent triazine organic framework materials and its preparation method and application with fluorine-triphenylamine structure
CN109942814A (en) * 2019-03-14 2019-06-28 东华大学 A kind of conjugation microporous polymer and its preparation method and application containing pyridyl group
CN110218301A (en) * 2019-07-15 2019-09-10 台州学院 One kind being based on the organic microporous polymer of conjugation and preparation method thereof of 1,3,5- tri- (4- Fonnylphenyl) benzene
CN110364370A (en) * 2019-06-19 2019-10-22 东华大学 A kind of pyridyl group porous carbon material and its preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109880087A (en) * 2019-03-13 2019-06-14 福州大学 A kind of covalent triazine organic framework materials and its preparation method and application with fluorine-triphenylamine structure
CN109942814A (en) * 2019-03-14 2019-06-28 东华大学 A kind of conjugation microporous polymer and its preparation method and application containing pyridyl group
CN110364370A (en) * 2019-06-19 2019-10-22 东华大学 A kind of pyridyl group porous carbon material and its preparation method and application
CN110218301A (en) * 2019-07-15 2019-09-10 台州学院 One kind being based on the organic microporous polymer of conjugation and preparation method thereof of 1,3,5- tri- (4- Fonnylphenyl) benzene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111841509A (en) * 2020-07-08 2020-10-30 东华大学 High CO2Selective polymer adsorbent and preparation method thereof
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
CN114849778A (en) * 2021-02-04 2022-08-05 湖南大学 Silver-loaded catalyst of hydrophilic bipyridyl conjugated microporous polymer and preparation method and application thereof
CN114849778B (en) * 2021-02-04 2023-06-20 湖南大学 Hydrophilic bipyridyl conjugated microporous polymer supported silver catalyst and preparation method and application thereof

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