CN109232781B - Preparation method of nitrogen-containing porous organic polymer - Google Patents
Preparation method of nitrogen-containing porous organic polymer Download PDFInfo
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- CN109232781B CN109232781B CN201811103897.5A CN201811103897A CN109232781B CN 109232781 B CN109232781 B CN 109232781B CN 201811103897 A CN201811103897 A CN 201811103897A CN 109232781 B CN109232781 B CN 109232781B
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229920000620 organic polymer Polymers 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 14
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002841 Lewis acid Substances 0.000 claims abstract description 4
- 230000029936 alkylation Effects 0.000 claims abstract description 4
- 238000005804 alkylation reaction Methods 0.000 claims abstract description 4
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 4
- 238000007171 acid catalysis Methods 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- 239000011968 lewis acid catalyst Substances 0.000 claims description 11
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 7
- 239000000376 reactant Substances 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 5
- 238000000967 suction filtration Methods 0.000 claims description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical group NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 230000006698 induction Effects 0.000 claims 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims 1
- 230000037396 body weight Effects 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 40
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 27
- 239000007789 gas Substances 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000003463 adsorbent Substances 0.000 abstract description 9
- 239000001569 carbon dioxide Substances 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract description 2
- 239000002440 industrial waste Substances 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 26
- 229910052757 nitrogen Inorganic materials 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 229960004011 methenamine Drugs 0.000 description 7
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical compound C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- -1 1, 4-dichlorobenzyl Chemical group 0.000 description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N hydrochloric acid Substances Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- 229910003074 TiCl4 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by heteroatoms or groups containing heteroatoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J20/22—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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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/02—Polyamines
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0627—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
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Abstract
本发明涉及一种环境催化剂的制备及其应用，具体涉及一种含氮多孔有机聚合物的制备方法及其在CO2吸附与转化方面的应用。本发明在路易斯酸催化条件下，选择含氮单体与1,4‑对二氯苄或乙烯基苄基氯通过烷基化诱导交联来合成含氮的多孔有机聚合物。其得到的含氮聚合物具有稳定的含氮活性位点，较大比例的介孔大孔，独特的二氧化碳富集特性、较高的CO2/N2选择性，使得N‑POPs吸附剂在工业废气中进行CO2高选择性吸附具有良好的应用前景。
The invention relates to the preparation and application of an environmental catalyst, in particular to a preparation method of a nitrogen-containing porous organic polymer and its application in CO 2 adsorption and conversion. The invention selects nitrogen-containing monomers and 1,4-p-dichlorobenzyl or vinylbenzyl chloride to induce crosslinking through alkylation under Lewis acid catalysis conditions to synthesize nitrogen-containing porous organic polymers. The obtained nitrogen-containing polymer has stable nitrogen-containing active sites, a large proportion of mesopores and macropores, unique carbon dioxide enrichment characteristics, and high CO2 / N2 selectivity, which makes N-POPs adsorbents in The highly selective adsorption of CO2 in industrial waste gas has good application prospects.
Description
Technical Field
The invention relates to preparation and application of an environmental catalyst, in particular to a preparation method of a nitrogen-containing porous organic polymer and application thereof in CO2The application of adsorption and conversion.
Background
After entering the industrial era from the world, the increasing concentration of carbon dioxide in the atmosphere and the resulting climate and environmental problems such as global warming and ocean acidification are receiving attention. The emission of acid gases such as carbon dioxide mainly comes from industrial activities, which mainly depend on the use of fossil fuels, for example, a great amount of carbon dioxide is removed from the tail gas of water gas shift reaction in coal gasification industry, so it is very important to eliminate carbon dioxide from industrial tail gas to alleviate various environmental problems. At present, the amine solution is due to the CO2Has been widely used for CO at low cost and reversible chemical reaction2Is selected fromAnd (4) selectively capturing. But has the problems of great solvent volatilization loss, serious corrosion of equipment and the like. Therefore, an efficient and pollution-free adsorption medium was developed to replace amine solutions for CO2Selective capture is important.
In recent years, scientists have conducted extensive research work on the selective capture of CO from industrial flue gases2The porous material is used as an absorbent, and the materials have the advantages of no volatility, no corrosion, easy regeneration and the like. Porous Organic Polymers (POPs), one of the most advanced materials, attract extensive attention of researchers due to their diversification in construction and synthesis routes, thereby providing an idea for structural and functional design. Furthermore, POPs covalently bound to them generally have high physical and chemical stability. Thus, POPs are in CO2Has great application potential in capture. However, POPs are on CO2The capture performance of (a) depends not only on its structural properties but also on the active sites it has. Specific functional groups, particularly nitrogen sites, are introduced into the POPs framework, so that the CO content of the POPs can be greatly improved2Capture efficiency due to CO2Unique Lewis acid-base interaction with nitrogen sites to achieve higher CO2/N2And (4) selectivity.
Much research is currently done on CO2The adsorbent mainly comprises active carbon, alumina, molecular sieve, silicon dioxide and the like. Patent No. CN107661748A discloses an organic amine functionalized macroporous silica CO2The adsorbent is organic amine functional macroporous silicon dioxide CO formed by taking organic amine as an active component2CO of adsorbent2The adsorption capacity is greatly improved, the dynamic adsorption capacity reaches 208mg/g, and the regeneration cycle stability is good. But the organic amine in the functionalization process can affect human bodies and the environment, thereby influencing the further application and development of the adsorbent. Patent No. CN108079956A discloses a novel multi-stage micro/mesoporous solid amine adsorbent, which is prepared by mixing HZSM-5 and MCM-41 according to different mass ratios to obtain a composite molecular sieve carrier, and taking Tetraethylenepentamine (TEPA) as a modifier, wherein when the mass ratio of the HZSM-5 to the MCM-41 is 1: 1, the TEPA loading amount is 30%, and the adsorption temperature is highWhen the temperature is 55 ℃ and the air inlet flow is 30mL/min, the equilibrium adsorption amount is up to 3.57mmol/g, and after 10 times of adsorption and desorption cycles, the adsorption amount is reduced by 8.1 percent. Although the above adsorbent also has a good adsorption effect, it requires activation with an organic amine to obtain its active site, resulting in a lack of stability of its adsorption performance. Therefore, under the catalysis of Lewis acid, the nitrogen-containing monomer and 1, 4-p-dichlorobenzyl are selected to synthesize the nitrogen-containing porous organic polymer through alkylation induced crosslinking. The obtained nitrogen-containing polymer has stable nitrogen-containing active sites, a large proportion of mesoporous macropores, unique carbon dioxide enrichment characteristic and high CO2/N2Selectively, the N-POPs adsorbent is subjected to CO in the industrial waste gas2The high-selectivity adsorption has good application prospect.
Disclosure of Invention
The invention aims to overcome the problems of insufficient adsorption capacity and poor stability of the existing adsorbent, and provides a preparation method of a high-nitrogen-content mesoporous macroporous organic polymer.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a nitrogen-containing porous polymer material comprises the following steps:
a. dissolving a certain mass of 1, 4-p-dichlorobenzyl or vinylbenzyl chloride in 1, 2-dichloroethane, wherein when the vinylbenzyl chloride is used as a raw material, an initiator azobisisobutyronitrile AIBN (azodiisobutyronitrile) is required to be added; then vigorously stirring for 30-120s at 0 deg.C, and adding a certain volume of Lewis acid catalyst into the mixture;
b. subsequently, adding a certain mass of nitrogen-containing monomer to the mixture;
c. in N2Heat treating for a period of time in an atmosphere;
d. the solid formed is filtered off and washed thoroughly with hot anhydrous ethanol to remove residual reactants and lewis acid catalyst;
e. immersing the crude product in isopropylamine, treating at room temperature for 6-12h for activation, and then drying in vacuum;
preferably, the mass of the 1, 4-dichlorobenzyl in the step a is 0.5-2g, and the volume of the 1, 2-dichloroethane is 15-30 ml; the volume of vinylbenzyl chloride is 0.5-1.5 ml, and the mass of the initiator is 0.05g
Preferably, the volume of the Lewis acid catalyst in the step a is 2-5ml, and the type of the Lewis acid catalyst is SnCl4Or TiCl4。
Preferably, in the step b, the mass of the nitrogen-containing monomer is 0.5-1.5g, and the nitrogen-containing monomer is one of p-phenylenediamine, 4,4' -bipyridine, hexamethylenetetramine or 4-vinylpyridine.
Preferably, the heat treatment temperature of the step c is 60-90 ℃, and the heat treatment time is 2-6 h.
Preferably, in the step d, the number of times of washing with ethanol is 6-12.
Preferably, in the step e, the temperature of vacuum drying is 60-120 ℃ and the time is 6-24 h.
A nitrogen-containing porous organic polymer is prepared by the method, and the porous nitrogen-containing polymer is used for selectively adsorbing carbon dioxide with high efficiency.
Preferably, the porous nitrogen-containing polymer is used for CO2In N2Selective adsorption of (1).
Preferably, the CO is2The adsorption temperatures of (A) were 0 ℃ and 25 ℃.
Preferably, the sorbent loading is 0.1 g; pretreating under vacuum condition at 160 deg.C for 12 hr before adsorption, and placing in Dewar flask at 0 deg.C and 25 deg.C for CO2And N2Adsorption of (3).
The invention has the following advantages and beneficial effects:
1. the nitrogen-containing porous polymer has strong adjustability, high material thermal stability, simple and green preparation process, easy realization of industrial production and wide application prospect.
2. The surface area of the nitrogen-containing porous organic polymer is as high as 700-1200 m2Per g, has good activity and selectivity in carbon dioxide adsorptionSex;
3. the nitrogen-containing porous organic polymer material prepared by the invention does not need to load or add other active components, and nitrogen elements contained in the material can improve the surface alkalinity of the material, increase the number of carbon edge positions and defect positions and strengthen the adsorption of carbon dioxide.
Drawings
FIG. 1 shows examples 1 to 4 of the present invention in which CO is present at 0 ℃2And N2The adsorption curve of (c);
FIG. 2 shows examples 1 to 4 of the present invention in which CO is present at 25 ℃2And N2The adsorption curve of (c);
FIG. 3 is CO of example 2 of the present invention2Performing a cyclic adsorption experiment; (adsorption conditions: pure CO)2At 25 ℃, 50mL/min for 180 min; the desorption conditions are as follows: pure N2, 75 ℃，150 mL/min, 120 min）；
FIG. 4 shows N at liquid nitrogen temperature for nitrogen-containing porous organic polymers in examples 1 to 4 of the present invention2A physical adsorption-desorption curve;
FIG. 5 is a diagram showing the pore size distribution of porous organic nitrogen-containing polymers in examples 1 to 4 of the present invention;
FIG. 6 is an SEM image of porous nitrogen-containing organic polymers of examples 1 to 4 of the present invention; the a figure is N-POP-p-phenylenediamine, the b figure is N-POP-4,4' -bipyridyl, the c and d figures are N-POP-hexamethylene tetramine, and the e and f figures are N-POP-pyridine.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in detail below with reference to examples and accompanying drawings, which are provided for further illustration of the present invention and are not intended to limit the present invention.
Example 1
N-POP-p-phenylenediamine: 0.5g of 1, 4-p-dichlorobenzyl was dissolved in 20ml of 1, 2-dichloroethane, which was then stirred vigorously at 0 ℃ for 60s, and 2ml of SnCl was added to the mixture4.1g of p-phenylenediamine monomer is then added to the mixture in N2The reaction was carried out at 70 ℃ for 3h under an atmosphere. The solid formed after suction filtration was then washed 8 times with hot anhydrous ethanol to remove residual reactants and lewis acidA catalyst. Finally, the crude product is immersed in isopropylamine, treated for 12h at room temperature for activation, dried in vacuum at 80 ℃ for 18h to obtain a nitrogen-containing porous organic polymer, namely N-POP-p-phenylenediamine, and the specific surface area of the sample is 1116m2The content of nitrogen element is 3.5 percent per gram.
Example 2
N-POP-4,4' -bipyridine: 2.0g of 1, 4-dichlorobenzyl are dissolved in 25ml of 1, 2-dichloroethane, stirred vigorously at 0 ℃ for 30s and 4ml of TiCl are added to the mixture4. 1.5g N-POP-4,4' -bipyridine monomer was then added to the mixture in N2The reaction is carried out for 5h at 90 ℃ under the atmosphere. The solid formed after suction filtration was then washed 9 times with hot anhydrous ethanol to remove residual reactants and lewis acid catalyst. Finally, immersing the crude product in isopropylamine, treating for 9h at room temperature for activation, and drying in vacuum at 100 ℃ for 12h to obtain a nitrogen-containing porous organic polymer which is marked as N-POP-4,4' -bipyridyl. The specific surface area of this sample was 1047m2The content of nitrogen element is 5.1 percent per gram.
Example 3
N-POP-hexamethylenetetramine: 1.0 g of 1, 4-p-dichlorobenzyl was dissolved in 30ml of 1, 2-dichloroethane, which was then stirred vigorously at 0 ℃ for 90s, and 3ml of SnCl was added to the mixture4. 0.85 g N-POP-hexamethylenetetramine monomer was then added to the mixture in N2The reaction was carried out at 75 ℃ for 3h under an atmosphere. The solid formed after suction filtration was then washed 6 times with hot anhydrous ethanol to remove residual reactants and lewis acid catalyst. And finally, immersing the crude product in isopropylamine, treating for 6h at room temperature for activation, and drying in vacuum at 70 ℃ for 24h to obtain a nitrogen-containing porous organic polymer, namely N-POP-hexamethylenetetramine. The specific surface area of this sample was 1177m2The content of nitrogen element is 3.3 percent per gram.
Example 4
N-POP-pyridine: 1mL of vinylbenzyl chloride and 0.78mL of 4-vinylpyridine were dispersed in 30mL of 1, 2-dichloroethane, followed by the addition of 0.05g of azobisisobutyronitrile AIBN initiator. The copolymerization is carried out by heating the mixture at 80 ℃ for 24 hours to give a viscous copolymer with linear characteristics. To obtain a hypercrosslinked network, it was then stirred vigorously at 0 ℃ for 90s and 4mL of TiCl were added4Is introduced into the mixture and is in N2Under the protection of atmosphere, the reaction is carried out at 90 ℃ for 6 hours. The resulting solid was filtered off and washed with hot anhydrous ethanol and hydrochloric acid to remove residual reactants and lewis acid catalyst. The crude product was then immersed in isopropylamine, treated at room temperature for 12h for activation, and then dried under vacuum at 80 ℃ for an additional 12 h. The synthesized sample is denoted as N-POP-pyridine. The specific surface area of this sample was 969 m2The content of nitrogen element is 3.0 percent per gram.
Comparative example 1
POP without nitrogen doping: 2.0g of 1, 4-dichlorobenzyl are dissolved in 15mL of 1, 2-dichloroethane, stirred vigorously at 0 ℃ and 5mL of TiCl are added to the mixture4. Then, in N2The reaction was carried out at 75 ℃ for 24 hours under an atmosphere. The solid formed by suction filtration was washed with hot absolute ethanol to remove residual reactants and lewis acid catalyst and dried under vacuum at 80 ℃ for 24 hours. The sample was designated as POP. The specific surface area of this sample was 592 m2/g。
Comparative example 2
PDVB-VP porous organic polymer: 0.065 g of azobisisobutyronitrile was weighed out and dissolved in 25mL of ethyl acetate, and then 2mL of Divinylbenzene (DVB) and 1mL of 4-Vinylpyridine (VP) were added successively, and after stirring at room temperature for 3 hours, all the mixtures were put in a pot at 120 ℃ and treated for 24 hours. After completion of the reaction, the solvent was evaporated at room temperature for 24h and the resulting solid was dried under vacuum at 80 ℃ for 24h to give a pale pink powder. The synthetic porous organic polymer is represented by PDVB-VP-0.5, where 0.5 is the volume ratio VP/DVB. The specific surface area of the polymer was 479m2In terms of a/g, the nitrogen content was 4.18%.
CO2Adsorption Performance and selectivity test
Prior to testing, the samples were treated at 160 deg.C (0.1 Pa) for 12 h. Then transferred to a Mac 3020 physical adsorption apparatus and tested for CO at 0 and 25 deg.C, respectively2And N2Adsorption isotherm of (1). And CO2The cyclic adsorption experiment of (A) was carried out in a Mettler TGA/SDTA 851eAbout 5mg (accurately weighed) of the sample was placed in a ceramic crucible and transferred to a TGA balance. When the sample was stable at 25 ℃, the gas was purged with nitrogen (150 ml/min) for 30 minutes and then switched to pure CO2Gas (50 ml/min) and hold for 2 h. Subsequently, CO is introduced2Gas switching to N2And the temperature was raised to 75 ℃. CO 22The cycle experiment of adsorption was tested 10 times after the temperature and airflow were stable.
TABLE 1 samples of N-POPs CO at different temperatures and pressures2Adsorption amount and CO2/N2IAST selectivity
[a]According to the mixture gas CO2/N2(0.15/0.85) was calculated from the IAST model at 1 bar.
FIGS. 1-2 show the measurement of CO at 0 ℃ and 25 ℃ for examples and comparative examples2And N2Adsorption isotherms. The CO at different temperatures and pressures is summarized in Table 12Adsorption capacity and selectivity thereof. As can be seen from the graph, N-POP-hexamethylene tetramine has higher CO2Adsorption capacities (5.67 and 3.93mmol/g at 1 bar at 0 ℃ and 25 ℃ respectively) for CO corresponding to POP2CO with adsorption capacities of 1.05 and 0.96 mmol/g, PDVB-VP-0.52The adsorption capacities are 1.84 and 1.48 mmol/g, which are both significantly lower than the N-POP-xCO of2And (4) adsorption performance. The addition of the nitrogen-containing monomer is illustrated, more nitrogen active sites are provided, and therefore, the CO of the material is greatly improved2And (4) adsorption performance. CO removal2Adsorption of CO in addition to its capacity2/N2The selectivity is also a very important parameter, and Table 1 gives the examples and comparative examples for CO2And N2(0.15/0.85 v/v) CO of the gas mixture2/N2Adsorption selectivity, calculated according to ideal solution adsorption theory (IAST). The selectivity of the examples is obviously higher than that of the comparative examples, and particularly, the selectivity of the N-POP-4,4' -bipyridyl at 0 ℃ and 25 ℃ is respectively as high as 73.9 and 75.6. Illustrating the nitrogen produced in this exampleThe porous polymer has good CO2Selective adsorption performance. The cycling experiment of N-POP-hexamethylene tetramine in figure 2 also proves that the material has good stability.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
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