CN111269417B - 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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CN111269417B
CN111269417B CN201911170206.8A CN201911170206A CN111269417B CN 111269417 B CN111269417 B CN 111269417B CN 201911170206 A CN201911170206 A CN 201911170206A CN 111269417 B CN111269417 B CN 111269417B
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microporous polymer
conjugated microporous
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pyridyl
polymer
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CN111269417A (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 conjugated microporous polymer containing pyridyl and a preparation method and application thereof. 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 adsorption separation material synthesis, and particularly relates to a conjugated microporous polymer containing pyridyl 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, pore structure controllability, 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 CO 2 The porous material being adsorbed by, in general, C-C metal coupling method, high price and CO 2 The selectivity of (2) is poor, and the adsorption capacity is required to be improved; therefore, it is necessary to develop a material which is low in cost, high in adsorptivity and low in consumption to replace the existing material.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the conjugated microporous polymer containing the pyridyl, and the preparation method and application thereof.
In order to solve the technical problems, the invention provides a conjugated microporous polymer containing pyridyl, which is synthesized by condensing and conjugated addition of two carbonyl-containing aromatic compounds in pyridine environment and cyclization with ammonia to form pyridine rings.
The technical scheme of the invention is as follows:
further, in the above-mentioned conjugated microporous polymer containing a pyridyl group, the aromatic compound containing a carbonyl group 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 containing a carbonyl group are as follows: the molar ratio of ketone groups=1:2.
In the conjugated microporous polymer containing pyridyl, 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 carbonyl-containing aromatic compounds aromatic aldehyde compounds with aromatic ketone compounds, adding ammonium acetate and pyridine, placing in an oil bath to react at a certain temperature and rotating speed, filtering, washing and vacuum drying to obtain the target product of the conjugated microporous polymer containing pyridyl.
The technical scheme of the invention is as follows:
further, in the preparation method of the conjugated microporous polymer containing pyridyl, the ammonium acetate is prepared by the following molar ratio: carbonyl-containing aromatic compound=10:1.
In the preparation method of the conjugated microporous polymer containing the pyridyl, the conjugated microporous polymer is placed in an oil bath pot to be heated and stirred for reaction for 12-24 hours at the temperature of 110-120 ℃.
In the preparation method of the conjugated microporous polymer containing the pyridyl, deionized water and an organic solvent are adopted to wash at 60-80 ℃ in sequence during washing, and the washing time is 24 hours.
In the preparation method of the conjugated microporous polymer containing the pyridyl, the organic solvent is at least one of DMSO, methanol and chloroform.
In the preparation method of the conjugated microporous polymer containing the pyridyl, the technological parameters of vacuum drying are as follows: the vacuum drying temperature is 60-100deg.C, and the vacuum drying time is 20-24h.
Preferably, the volume of pyridine added is 100-200mL.
The invention also designs an application of the conjugated microporous polymer containing the pyridyl group, which is used as a carbon dioxide adsorbent for adsorbing and separating carbon dioxide.
The beneficial effects of the invention are as follows:
the invention adopts two carbonyl-containing aromatic compounds as reaction monomers to carry out condensation and conjugate addition in pyridine environment, and simultaneously cyclizes with ammonia to form pyridine rings, so as to synthesize pyridine nitrogen-doped conjugated microporous polymers, and the polymers have potential application values in the fields of gas adsorption and separation, energy storage, catalysis, electrochemistry and the like.
Synthesized according to the invention as CO 2 The method for preparing the conjugated microporous polymer containing pyridyl of the adsorbent comprises the steps of introducing pyridyl to provide selective adsorption, wherein the existence of pyridine ring provides rigidity, thermal stability and chemical stability for the polymer, and can be used as an affinity active site to achieveThe purpose of adsorbing gas; the specific surface area and the pore structure are optimized by changing the construction unit, so that the adsorption capacity is improved; and the non-metal coupling is low in cost.
Drawings
FIG. 1 is a FTIR of a pyridinyl group-containing conjugated microporous polymer 1 synthesized in example 1;
FIG. 2 is N at 77.4K of the pyridyl group containing conjugated microporous polymer 1 synthesized in example 1 2 Adsorption-desorption curves of (a);
FIG. 3 is a schematic representation of a pyridyl group-containing conjugated microporous polymer 2 synthesized in example 2 13 C-NMR chart
FIG. 4 is a graph of CO at 273K for the pyridinyl group-containing conjugated microporous polymer 2 synthesized in example 2 2 Adsorption-desorption curves;
FIG. 5 is a graph of CO at 273K for the pyridine/bipyridine-containing conjugated microporous polymer 2 synthesized in example 2 2 N 2 Is a slope curve of the initial adsorption;
FIG. 6 is N at 77.4K of the pyridyl group containing conjugated microporous polymer 3 synthesized in example 3 2 Adsorption-desorption curves of (a);
FIG. 7 is a graph of CO at 298K of a pyridinyl group-containing conjugated microporous polymer 3 synthesized in example 3 2 Adsorption-desorption curves;
FIG. 8 is a graph of CO at 298K of the pyridyl group-containing conjugated microporous polymer 3 synthesized in example 3 2 N 2 Is a slope curve of the initial adsorption;
FIG. 9 is N at 77.4K of the pyridyl group containing conjugated microporous polymer 4 synthesized in example 4 2 Adsorption-desorption curves of (a);
FIG. 10 is a graph of CO at 298K of the pyridyl group-containing conjugated microporous polymer 4 synthesized in example 4 2 Adsorption-desorption curves;
FIG. 11 is a graph of CO at 298K of the pyridyl group-containing conjugated microporous polymer 4 synthesized in example 4 2 N 2 Is a slope curve of the initial adsorption;
FIG. 12 is N at 77.4K of a conjugated microporous polymer containing pyridyl groups synthesized in example 5 2 Adsorption-desorption curves of (a);
FIG. 13 is example 5CO at 298K of synthetic pyridinyl group-containing conjugated microporous polymer 5 2 Adsorption-desorption curves;
FIG. 14 is a graph of CO at 298K of the pyridyl group-containing conjugated microporous polymer 5 synthesized in example 5 2 N 2 Is a graph of the initial adsorption slope of (c).
Description of the embodiments
The invention will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. Further, it is understood that various changes and modifications may be made by those skilled in the art after reading the teachings of the present invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Example 1
The specific preparation method of the conjugated microporous polymer containing pyridyl provided by the embodiment is as follows: 1, 4-diacetylbenzene (243.3 mg,1.5 mmol) and tris- (4-formylphenyl) amine (164.7 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, then 100ml of pyridine was added to dissolve all the above mixed powder, and finally the mixture was placed in an oil bath at 115℃and stirred 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 24 hours, drying in a vacuum oven at 60 ℃ for 24 hours after the suction filtration to obtain a conjugated microporous polymer containing pyridyl, namely a polymer 1, wherein the BET specific surface area is 304m 2 /g。
The infrared spectrum of the polymer 1 obtained in this example is shown in fig. 1, and the peaks at 1678 and 1667 of the two c=o of the reaction monomers are significantly reduced, which proves that the aldehyde and ketone groups of the two monomers react, and a new peak at 1589 of c=n appears, indicating the possibility of forming a pyridine ring.
Polymer 1 obtained in this example was N at 77.4K 2 As shown in FIG. 2, the adsorption/desorption curve of (C) shows that the adsorption isotherm is in the low relative pressure region (P/P 0 <0.001 A rapid rise in the curve, indicating a faster gas adsorption due to the presence of microporesIndicating the presence of a certain microporous structure in polymer 1; in the medium-high relative pressure region (P/P 0 =0.1 to 1.0), the curve rises at a slower rate, indicating the presence of macropores in polymer 1. The final desorption and adsorption curves were not completely closed, possibly due to a small amount of N 2 Residual in the pores of polymer 1 is not completely desorbed.
Example 2
The specific preparation method of the conjugated microporous polymer containing pyridyl provided by the embodiment is as follows: 1, 4-diacetylbenzene (243.3 mg,1.5 mmol) and 2,4, 6-tris (4-aldehydophenyl) -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, then 100ml pyridine was added to dissolve all the above mixed powder, and finally the mixed solution was placed in 115℃oil bath temperature and stirred for reaction for 24 hours. After the reaction is finished, carrying out suction filtration in a sand core funnel, respectively stirring and washing with deionized water (60 ℃), DMSO (80 ℃), methanol (60 ℃) and chloroform (60 ℃) for 24 hours, carrying out suction filtration, and then drying in a vacuum oven at 60 ℃ for 24 hours to obtain the conjugated microporous polymer containing pyridyl, namely polymer 2, wherein the BET specific surface area is 325m 2 /g。
Polymer 2 obtained in this example 13 The C-NMR test results 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 presence of the triazine ring; the peak at the chemical shift of 137.1ppm is the peak of C at the para position in the pyridine ring, demonstrating the reaction to form pyridinyl; the peak at the chemical shift of 127.7ppm is the peak of C in the chemical environment of the benzene ring, demonstrating the presence of the conjugated structure. This result confirms the successful synthesis of polymer 2.
This example gives CO at 273K for Polymer 2 2 The adsorption and desorption curves are shown in fig. 4, and the adsorption curves can be rapidly increased in the low-pressure area, which shows that the microporous structure of the polymer has a certain effect on CO2 adsorption. CO of Polymer 2 at 273K,1 Bar 2 The adsorption amount reaches 7.09wt%. CO at this temperature 2 The desorption curve and the adsorption curve completely coincide, which shows that the obtained polymer 2 is a polymerIn CO 2 Is reversible.
CO at 273K for Polymer 2 obtained in this example 2 N 2 The initial adsorption slope curve of (2) is shown in FIG. 5, and the fitted CO is calculated 2 N 2 The ratio of the initial adsorption curve slope can be known to be CO 2 /N 2 The adsorption selectivity is 32.4, and the adsorption selectivity is good.
Example 3
The specific preparation method of the conjugated microporous polymer containing pyridyl provided by the embodiment is as follows: 1,3, 5-triacetyl benzene (408.5 mg,2 mmol) and 1,3, 5-tris (p-formylphenyl) benzene (390.4 mg,1 mmol) were mixed at normal temperature and pressure in a 200ml round bottom flask, ammonium acetate (2.31 g,30 mmol) was added, then 100ml 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, respectively stirring and washing with deionized water, methanol and chloroform at 60 ℃ for 24 hours, drying in a vacuum oven at 60 ℃ for 24 hours after the suction filtration to obtain a conjugated microporous polymer containing pyridyl, namely a polymer 3, wherein the BET specific surface area is 511m 2 /g。
Polymer 3 obtained in this example was N at 77.4K 2 As shown in FIG. 6, the adsorption/desorption curve of (C) shows that the adsorption isotherm is in the low relative pressure region (P/P 0 <0.001 The curve rises rapidly, indicating a faster gas adsorption due to the presence of micropores, indicating a certain microporous structure in the polymer 3; in the medium-high relative pressure region (P/P 0 =0.1 to 1.0), the curve rises at a slower rate, indicating the presence of macropores in polymer 3. The final desorption and adsorption curves were not completely closed, possibly due to a small amount of N 2 Residual in the pores of the polymer 3 is not completely desorbed.
This example gives CO at 298K for Polymer 3 2 The adsorption and desorption curves are shown in fig. 7, and the adsorption curves can be rapidly increased in the low-pressure area, which shows that the microporous structure of the polymer has a certain effect on the adsorption of CO 2. Polymerization under 298K,1 BarCO of Compound 2 2 The adsorption amount reaches 5.74wt%. CO at this temperature 2 The desorption curve and the adsorption curve completely coincide, which shows that the obtained polymer 3 is specific to CO 2 Is reversible.
The polymer 3 obtained in this example was CO at 298K 2 N 2 The initial adsorption slope curve of (2) is shown in FIG. 8, and the fitted CO is calculated 2 N 2 The ratio of the initial adsorption curve slope can be known to be CO 2 /N 2 The adsorption selectivity is 29.1, and the adsorption selectivity is good.
Example 4
The specific preparation method of the conjugated microporous polymer containing pyridyl provided by the embodiment is as follows: 1,3, 5-Triacetophenone (408.5 mg,2 mmol) and tris- (4-formylphenyl) amine (329.4 mg,1 mmol) were mixed at normal temperature and pressure in a 200ml round bottom flask, ammonium acetate (2.31 g,30 mmol) was added, then 100ml pyridine was added to dissolve all the above mixed powder, and finally the mixture was stirred at 115℃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 24 hours, drying in a vacuum oven at 60 ℃ for 24 hours after the suction filtration to obtain a conjugated microporous polymer containing pyridyl, namely a polymer 4, wherein the BET specific surface area is 523m 2 /g。
Polymer 4 obtained in this example was N at 77.4K 2 As shown in FIG. 9, the adsorption/desorption curve of (C) is shown in the low relative pressure region (P/P 0 <0.001 The curve rises rapidly, indicating a faster gas adsorption due to the presence of micropores, indicating a certain microporous structure in the polymer 3; in the medium-high relative pressure region (P/P 0 =0.1 to 1.0), the curve rises at a slower rate, indicating the presence of macropores in polymer 4. The final desorption and adsorption curves were not completely closed, possibly due to a small amount of N 2 Residual in the pores of the polymer 3 is not completely desorbed.
This example gives CO at 298K for Polymer 4 2 The adsorption and desorption curves are shown in FIG. 10The adsorption curve is known to rise rapidly 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 Bar 2 The adsorption amount reaches 4.90wt%. CO at this temperature 2 The desorption curve and the adsorption curve completely coincide, which shows that the obtained polymer 4 is specific to CO 2 Is reversible.
The polymer 4 obtained in this example was CO at 298K 2 N 2 The initial adsorption slope curve of (a) is shown in FIG. 11, and the fitted CO is calculated 2 N 2 The ratio of the initial adsorption curve slope can be known to be CO 2 /N 2 The adsorption selectivity is 40.6, and the adsorption selectivity is good.
Example 5
The specific preparation method of the conjugated microporous polymer containing pyridyl provided by the embodiment is as follows: 1,3, 5-triacetyl benzene (204.3 mg,1 mmol) and 2,4, 6-tris (4-aldehydylphenyl) -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, then 100ml pyridine was added to dissolve all the above mixed powder, and finally the mixture was placed in 115 ℃ oil bath temperature and stirred for reaction for 24 hours. After the reaction is finished, carrying out suction filtration in a sand core funnel, stirring and washing for 24 hours in deionized water (60 ℃), DMSO (80 ℃), methanol (60 ℃) and chloroform (60 ℃), and drying for 24 hours in a vacuum oven at 60 ℃ after the suction filtration, thus obtaining the conjugated microporous polymer containing pyridyl, namely polymer 4, wherein the BET specific surface area of the conjugated microporous polymer is 515m 2 /g。
Polymer 5 obtained in this example was N at 77.4K 2 As shown in FIG. 12, the adsorption/desorption curve of (C) shows that the adsorption isotherm is in the low relative pressure region (P/P 0 <0.001 A rapid rise in the curve, indicating a faster gas adsorption due to the presence of micropores, indicating a certain microporous structure in the polymer 5; in the medium-high relative pressure region (P/P 0 =0.1 to 1.0), the curve rises at a slower rate, indicating the presence of macropores in polymer 5. The final desorption and adsorption curves were not completely closed, possibly due to a small amount of N 2 Residual in the pores of the polymer 3 is not completely desorbed.
This example gives CO at 298K for Polymer 5 2 The adsorption and desorption curves are shown in fig. 13, and the adsorption curves can be rapidly increased in the low-pressure area, which shows that the microporous structure of the polymer has a certain effect on CO2 adsorption. CO of Polymer 5 at 298K,1 Bar 2 The adsorption amount reaches 4.7wt%. CO at this temperature 2 The desorption curve and the adsorption curve completely coincide, which shows that the obtained polymer 4 is specific to CO 2 Is reversible.
The polymer 5 obtained in this example was CO at 298K 2 N 2 The initial adsorption slope curve of (2) is shown in FIG. 14, and the fitted CO is calculated 2 N 2 The ratio of the initial adsorption curve slope can be known to be CO 2 /N 2 The adsorption selectivity is 47.0, and the adsorption selectivity is good.
Synthesized according to the invention as CO 2 The method for preparing the pyridyl-containing conjugated microporous polymer of the adsorbent provides selective adsorption by introducing pyridyl, and the existence of pyridine rings 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 specific surface area and the pore structure are optimized by changing the construction unit, so that the adsorption capacity is improved; and the non-metal coupling is low in cost.
In addition to the embodiments described above, other embodiments of the invention are possible. All technical schemes formed by equivalent substitution or equivalent transformation fall within the protection scope of the invention.

Claims (7)

1. The preparation method of the pyridyl-containing conjugated microporous polymer is characterized by comprising the following specific preparation processes:
mixing an aromatic aldehyde compound and an aromatic ketone compound, 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 the mixture to obtain a target product of the conjugated microporous polymer containing pyridyl;
the aromatic ketone compound is 1, 4-diacetyl benzene or 1,3, 5-triacetyl benzene; 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 aromatic ketone compound and the aromatic aldehyde compound are prepared by the following aldehyde groups: mixing in a molar ratio of keto=1:2;
the ammonium acetate is as follows: the sum of aromatic aldehyde compound and aromatic ketone compound=10:1.
2. The method for preparing a pyridyl group-containing conjugated microporous polymer according to claim 1, wherein: heating and stirring in an oil bath at 110-120deg.C for reacting for 12-24 hr.
3. The method for preparing a pyridyl group-containing conjugated microporous polymer according to claim 1, wherein: the deionized water and the organic solvent are adopted in sequence for washing at the temperature of 60-80 ℃ during washing, and the washing time is 24 hours.
4. A method for preparing a pyridyl group-containing conjugated microporous polymer according to claim 3, wherein: the organic solvent is at least one of DMSO, methanol and chloroform.
5. The method for preparing a pyridyl group-containing conjugated microporous polymer according to claim 1, wherein: the technological parameters of the vacuum drying are as follows: the vacuum drying temperature is 60-100deg.C, and the vacuum drying time is 20-24h.
6. A pyridyl group-containing conjugated microporous polymer characterized by: is prepared by the preparation method of the conjugated microporous polymer containing pyridyl according to any one of claims 1-5.
7. Use of the pyridyl group-containing conjugated microporous polymer according to claim 6, wherein: as carbon dioxide adsorbent for adsorption and separation of carbon dioxide.
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