CN111154074B - Sulfonate porous aromatic skeleton material and application thereof - Google Patents

Sulfonate porous aromatic skeleton material and application thereof Download PDF

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CN111154074B
CN111154074B CN202010031192.8A CN202010031192A CN111154074B CN 111154074 B CN111154074 B CN 111154074B CN 202010031192 A CN202010031192 A CN 202010031192A CN 111154074 B CN111154074 B CN 111154074B
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paf
porous aromatic
aromatic skeleton
skeleton material
sulfonate
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CN111154074A (en
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邹小勤
张盼盼
杨柳
朱广山
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Northeast Normal University
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    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • 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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    • 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
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
    • B01D2253/20—Organic adsorbents
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
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    • B01D2257/102—Nitrogen
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/10—Definition of the polymer structure
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    • C—CHEMISTRY; METALLURGY
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    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/312—Non-condensed aromatic systems, e.g. benzene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C08G2261/722—Sulfonation

Abstract

The invention provides a sulfonate porous aromatic skeleton material and application thereof, belonging to the technical field of porous organic skeleton materials. The preparation method of the sulfonate porous aromatic skeleton material provided by the invention comprises the following steps: under the protective atmosphere, mixing an organic monomer, a nickel catalyst, a catalyst stabilizer and an anhydrous solvent, and carrying out Ullmann reaction to obtain a porous aromatic framework material; the organic monomer comprises tetrabromo tetraphenyl methane or 1,3, 5-tribromobenzene; mixing the porous aromatic skeleton material, a sulfonation reagent and a solvent, and carrying out sulfonation reaction to obtain a sulfonic group porous aromatic skeleton material; mixing the sulfonic acid group porous aromatic skeleton material, organic metal salt and a nitrile solvent, and carrying out an ion exchange reaction to obtain a sulfonate porous aromatic skeleton material; the metal ion in the organic metal salt comprises Ag + Or Cu + . The preparation method provided by the invention is simple to operate, and the sulfonate porous aromatic skeleton material has high selective adsorption on ethylene.

Description

Sulfonate porous aromatic skeleton material and application thereof
Technical Field
The invention relates to the technical field of porous organic framework materials, in particular to a sulfonate porous aromatic framework material and application thereof.
Background
Petrochemical industry is one of the prop industries promoting the economic development of the world, about 75 percent of petrochemical products are produced by ethylene at present, and the main petrochemical products comprise polyethylene, ethylene oxide, ethylene glycol, ethylbenzene and the like, so that the ethylene is a leading product of the petrochemical industry and is commonly called as a mother product of the petrochemical industry. The technology for producing ethylene mainly comprises the cracking reaction of paraffin oil and short-chain alkane, and the ethylene product produced by the technologyOften mixed with a plurality of byproducts (such as C) 2 H 6 ) Further purification is required. Currently, the industrially mature methods for separating ethylene and ethane include cryogenic rectification, adsorption separation and membrane separation. Among them, the adsorption separation has high selectivity, simple process and low cost, and is favored by the researchers.
Porous aromatic framework materials (PAFs) have the advantages of large specific surface, adjustable pore size, diversified structure and the like, and are widely concerned in the field of gas adsorption and separation. However, the pure porous aromatic skeleton material has poor selective adsorption performance on ethylene, and the selectivity of PAFs on ethylene can be improved by functionalizing the material (introducing metal ions). The existing porous aromatic skeleton material is difficult to be functionalized because of the stable structural nature formed by covalent bond connection.
Disclosure of Invention
In view of the above, the present invention aims to provide a sulfonate porous aromatic skeleton material, and a preparation method and applications thereof. The preparation method provided by the invention has simple process; and the prepared sulfonate porous aromatic skeleton material has high adsorption selectivity on ethylene.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a sulfonate porous aromatic skeleton material, which comprises the following steps:
under the protective atmosphere, mixing an organic monomer, a nickel catalyst, a catalyst stabilizer and an anhydrous solvent, and carrying out Ullmann reaction to obtain a porous aromatic framework material; the organic monomer comprises tetrabromo tetraphenyl methane or 1,3, 5-tribromobenzene; the specific surface area of the porous aromatic skeleton material is 1000-5600 m 2 /g；
Mixing the porous aromatic skeleton material, a sulfonation reagent and a solvent, and carrying out sulfonation reaction to obtain a sulfonic group porous aromatic skeleton material;
mixing the sulfonic acid group porous aromatic skeleton material, organic metal salt and a nitrile solvent, and carrying out an ion exchange reaction to obtain a sulfonate porous aromatic skeleton material; metal ion packet in the organometallic saltAg drawing + Or Cu + 。
Preferably, the nickel catalyst comprises one or more of 1, 5-cyclooctadiene nickel, tetrakis (triphenylphosphine) nickel and bis (triphenylphosphine) nickel bromide;
the catalyst stabilizer includes 2,2' -bipyridine and 1, 5-cyclooctadiene.
Preferably, the molar ratio of the organic monomer to the nickel catalyst to the catalyst stabilizer is 1 (3.5-18) to 3.5-18.
Preferably, the temperature of the Ullmann reaction is 80-140 ℃ and the time is 24-72 h.
Preferably, the sulfonating agent comprises chlorosulfonic acid, oleum, or concentrated sulfuric acid;
the mass ratio of the porous aromatic skeleton material to the sulfonation reagent is 1 (15-20).
Preferably, the temperature of the sulfonation reaction is 10-40 ℃, and the time is 12-72 hours.
Preferably, the organic metal salt comprises silver tetrafluoroborate or copper tetraacetonitrile tetrafluoroborate;
the mass ratio of the sulfonic acid group porous aromatic skeleton material to the organic metal salt is 1 (8-12).
Preferably, the temperature of the ion exchange reaction is 10-40 ℃, and the time is 72-144 h.
According to the sulfonate porous aromatic skeleton material prepared by the preparation method provided by the invention, metal ions in sulfonate comprise Ag + Or Cu + 。
The invention also provides application of the sulfonate porous aromatic skeleton material as a selective adsorption separating agent of ethylene.
The invention provides a preparation method of a sulfonate porous aromatic skeleton material, which comprises the following steps: under the protective atmosphere, mixing an organic monomer, a nickel catalyst, a catalyst stabilizer and an anhydrous solvent, and carrying out Ullmann reaction to obtain a porous aromatic framework material; the organic monomer comprises tetrabromo tetraphenyl methane or 1,3, 5-tribromobenzene; the specific surface area of the porous aromatic skeleton material is 1000-5600 m 2 (ii)/g; mixing the porous aromaMixing the framework material, a sulfonation reagent and a solvent, and carrying out sulfonation reaction to obtain a sulfonic acid group porous aromatic framework material; mixing the sulfonic acid group porous aromatic skeleton material, organic metal salt and a nitrile solvent, and carrying out an ion exchange reaction to obtain a sulfonate porous aromatic skeleton material; the metal ion in the organic metal salt comprises Ag + Or Cu + . The porous aromatic framework material is prepared firstly, the prepared porous aromatic framework material has large specific surface area and functional sites on the structure, and metal ions (Cu) are easily introduced after the porous aromatic framework material is sulfonated + Or Ag + ) Modifying it to incorporate Cu + And Ag + All have (n-1) d 10 ns 0 The electronic structure, the s-empty orbit can accept pi electrons in ethylene molecules, the d orbit can feed redundant electrons back to the pi-x orbit of ethylene to form a pi complex, the adsorption effect of the sulfonate porous aromatic skeleton material on ethylene is enhanced through the synergistic effect of sigma-pi, and the selective adsorption on ethylene is high. As shown in the results of the examples of the invention, the adsorption capacity of the sulfonate porous aromatic skeleton material provided by the invention on ethylene is up to 97.76cm 3 The heat of absorption per gram of ethylene is up to 73.02kJ/mol, and the separation coefficient of ethylene-ethane is up to 16.8.
Drawings
FIG. 1 is a carbon spectrum nuclear magnetic map of PAF-1 prepared in example 1;
FIG. 2 shows PAF-1 and PAF-1-SO prepared in example 1 3 H and PAF-1-SO 3 An infrared spectrogram of Cu;
FIG. 3 shows PAF-1 and PAF-1-SO prepared in example 1 3 H and PAF-1-SO 3 Thermogravimetric plot of Cu;
FIG. 4 shows PAF-1 and PAF-1-SO prepared in example 1 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 An adsorption curve diagram of Ag to nitrogen;
FIG. 5 shows PAF-1 and PAF-1-SO prepared in example 1 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 Adsorption curve diagram of Ag to ethane;
FIG. 6 is P prepared in example 1AF-1、PAF-1-SO 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 Adsorption curve diagram of Ag to ethylene;
FIG. 7 shows PAF-1 and PAF-1-SO prepared in example 1 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 Adsorption calorimetric diagrams of Ag on ethylene;
FIG. 8 shows PAF-1 and PAF-1-SO prepared in example 1 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 The selective adsorption of Ag to ethylene in an ethylene-ethane mixed system is shown in the figure;
FIG. 9 is a carbon spectrum nuclear magnetic map of PAF-67 prepared in example 3;
FIG. 10 shows PAF-67, PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 An infrared spectrogram of Cu;
FIG. 11 shows PAF-67, PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 Thermogravimetric plot of Cu;
FIG. 12 shows PAF-67, PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 Cu and PAF-67-SO prepared in example 4 3 An adsorption curve diagram of Ag to nitrogen;
FIG. 13 shows PAF-67, PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 Cu and PAF-67-SO prepared in example 4 3 Adsorption curve diagram of Ag to ethane;
FIG. 14 shows PAF-67, PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 Cu and PAF-67-SO prepared in example 4 3 Adsorption curve diagram of Ag to ethylene;
FIG. 15 shows PAF-67, PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 Cu and PAF-67-SO prepared in example 4 3 Adsorption calorimetric diagrams of Ag on ethylene;
FIG. 16 shows PAF-67 and PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 Cu and PAF-67-SO prepared in example 4 3 The selectivity of Ag to ethylene in an ethylene-ethane mixed system is shown in the figure.
Detailed Description
The invention provides a preparation method of a sulfonate porous aromatic skeleton material, which comprises the following steps:
under the protective atmosphere, mixing an organic monomer, a nickel catalyst, a catalyst stabilizer and an anhydrous solvent, and carrying out Ullmann reaction to obtain a porous aromatic framework material; the organic monomer comprises tetrabromo tetraphenyl methane or 1,3, 5-tribromobenzene; the specific surface area of the porous aromatic skeleton material is 1000-5600 m 2 /g；
Mixing the porous aromatic skeleton material, a sulfonation reagent and a solvent, and carrying out sulfonation reaction to obtain a sulfonic group porous aromatic skeleton material;
mixing the sulfonic acid group porous aromatic skeleton material, organic metal salt and a nitrile solvent, and carrying out an ion exchange reaction to obtain a sulfonate porous aromatic skeleton material; the metal ion in the organic metal salt comprises Ag + Or Cu + 。
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
Under the protective atmosphere, mixing an organic monomer, a nickel catalyst, a catalyst stabilizer and an anhydrous solvent, and carrying out Ullmann reaction to obtain a porous aromatic framework material; the organic monomer comprises tetrabromo tetraphenyl methane or 1,3, 5-tribromobenzene; the specific surface area of the porous aromatic skeleton material is 1000-5600 m 2 /g。
In the present invention, the nickel catalyst preferably comprises one or more of 1, 5-cyclooctadienenickel, tetrakis (triphenylphosphine) nickel and bis (triphenylphosphine) nickel bromide, more preferably comprises 1, 5-cyclooctadienenickel, tetrakis (triphenylphosphine) nickel or bis (triphenylphosphine) nickel bromide, and most preferably 1, 5-cyclooctadienenickel.
In the present invention, the catalyst stabilizer preferably includes 2,2' -bipyridine and 1, 5-cyclooctadiene. In the present invention, the molar ratio of 2,2' -bipyridine to 1, 5-cyclooctadiene is preferably 1 (1 to 10), more preferably 1 (1 to 5), and most preferably 1: 1. In the present invention, the 1, 5-cyclooctadiene is preferably subjected to a drying treatment before use; the reagent used in the drying treatment of the present invention is not particularly limited, and a dried 1, 5-ring known in the art can be usedA reagent of octadiene; in the examples of the present invention, CaH is preferably used 2 The 1, 5-cyclooctadiene is subjected to a drying treatment.
In the invention, the mol ratio of the organic monomer, the nickel catalyst and the catalyst stabilizer is preferably 1 (3.5-18) to 3.5-18. In the invention, when the organic monomer is tetrabromotetraphenyl methane, the molar ratio of the organic monomer, the nickel catalyst and the catalyst stabilizer is more preferably 1 (4.5-18): 4.5-18, and more preferably 1 (5-15): 5-15. In the invention, when the organic monomer is 1,3, 5-tribromobenzene, the molar ratio of the organic monomer, the nickel catalyst and the catalyst stabilizer is further preferably 1 (3.5-12) to (3.5-12), and more preferably 1 (5-10) to (5-10).
In the present invention, the protective atmosphere is preferably nitrogen, helium or argon, more preferably helium or argon.
In the present invention, the anhydrous solvent is preferably N, N '-dimethylformamide, N' -dimethylacetamide, N-methylpyrrolidone, benzene or toluene. In the present invention, the anhydrous solvent is preferably subjected to water removal and oxygen removal treatment before use. The water removal and oxygen removal operation of the anhydrous solvent is not particularly limited in the present invention, and may be performed by a method well known in the art. In the invention, the organic monomer has good solubility and stability in the anhydrous solvent, and other side reactions do not occur in the Ullmann reaction process. In the present invention, the ratio of the volume of the anhydrous solvent to the amount of the organic monomer is preferably 1mL (0.001 to 5) mmol, and more preferably 1mL (0.01 to 1) mmol.
In the present invention, the organic monomer, the nickel catalyst, the catalyst stabilizer, and the anhydrous solvent are preferably mixed in a manner of: firstly mixing a nickel catalyst, a catalyst stabilizer and a part of anhydrous solvent, and carrying out activation treatment to obtain an activated catalyst solution; secondly, mixing the organic monomer and the residual anhydrous solvent to obtain an organic monomer solution; and thirdly mixing the organic monomer solution with the activated catalyst solution. In the invention, the volume ratio of the partial anhydrous solvent to the residual anhydrous solvent is preferably (1-10): 1, and more preferably 4: 1.
In the invention, the temperature of the first mixing is preferably 80-140 ℃, more preferably 90-130 ℃, and most preferably 100-120 ℃; the time for the first mixing is preferably 30 to 60min, more preferably 35 to 55min, and most preferably 40 to 50 min. In the present invention, the first mixing is more preferably stirring mixing. The stirring and mixing speed in the present invention is not particularly limited, and a stirring speed well known in the art may be used. In the invention, the organic ligand in the catalyst can easily exchange with other ligands to generate Ni (pi-C) particularly with diene or triene 3 H 5 ) 2 Ni is not oxidized or reduced by alkene ligands, but 1, 5-cyclooctadiene (cod) has eight electrons entering the sp of nickel 3 The hybridization orbit leads the effective atomic number of the nickel to reach stable electronic configuration, thus adding the catalyst stabilizer to activate the catalyst and preventing other oxidation-reduction reactions from occurring.
In the present invention, the second mixing is further preferably ultrasonic mixing. The ultrasonic power of the ultrasonic mixing is not particularly limited, and the ultrasonic power well known in the field can be adopted; the temperature and time of the ultrasonic mixing are not particularly limited, and the organic monomer can be dissolved in the anhydrous solvent.
In the present invention, it is further preferable that the organic monomer solution is third mixed with the activated catalyst solution by adding the organic monomer solution to the activated catalyst solution. The rate of addition of the organic monomer solution is not particularly limited in the present invention, and may be any rate known in the art.
In the invention, the temperature of the Ullmann reaction is preferably 80-140 ℃, more preferably 90-130 ℃, and most preferably 100-120 ℃; the time of the Ullmann reaction is preferably 24-72 h, more preferably 30-60 h, and more preferably 36-48 h. In the invention, in the Ullmann reaction process, organic monomers react to generate the biaryl polymer.
The reaction formula of the Ullmann reaction of tetrabromotetraphenyl methane organic monomer is shown as the formula (1):
Figure BDA0002364350170000061
the reaction formula of the Ullmann reaction of the 1,3, 5-tribromobenzene organic monomer is shown as a formula (2):
Figure BDA0002364350170000062
after the Ullmann reaction, the invention preferably cools the reaction system obtained by the Ullmann reaction to room temperature in sequence, adjusts the pH value to 0-minus 0.78, and performs solid-liquid separation to obtain a solid product; and sequentially washing, Soxhlet extracting and drying the solid product to obtain the porous aromatic skeleton material.
In the invention, the reagent for adjusting the pH value is preferably hydrochloric acid aqueous solution; sulfuric acid, nitric acid and the like are not selected, and the concentration of the hydrochloric acid aqueous solution is preferably 6-12 mol/L, and more preferably 8-10 mol/L. In the present invention, the hydrochloric acid reacts with nickel in the nickel catalyst to generate + 2-valent hydrated nickel ions, thereby removing the nickel catalyst.
The solid-liquid separation mode is not particularly limited, and the solid-liquid separation known in the field can be adopted; in the practice of the present invention, the solid-liquid separation method is preferably suction filtration.
In the present invention, the washing preferably includes acid washing and water washing which are sequentially performed. In the invention, the acid reagent adopted by the acid washing is preferably hydrochloric acid aqueous solution, and the concentration of the hydrochloric acid aqueous solution is preferably 6-12 mol/L, and more preferably 8-10 mol/L; the number of times of pickling is preferably 2-3. In the invention, the water washing is preferably deionized water washing; the number of times of water washing is preferably 3 to 5 times. In the invention, the time for each washing is preferably 3-5 h. In the present invention, the washing can remove impurities adhered to the surface of the porous aromatic skeleton material.
In the present invention, the solvent used for the soxhlet extraction is preferably methanol, acetone or tetrahydrofuran; the time for Soxhlet extraction is preferably 24-36 h. The method utilizes strong polar organic solvent of methanol, acetone or tetrahydrofuran to extract, and can play a good role in purifying the porous aromatic skeleton material.
The drying method of the present invention is not particularly limited, and a drying method known in the art may be used. In the invention, the drying temperature is preferably 80-100 ℃, and more preferably 85-95 ℃; the drying time is preferably 4-48 h, and more preferably 10-30 h.
In the present invention, when the organic monomer is tetrabromotetraphenyl methane, the specific surface area of the porous aromatic skeleton material is preferably 4200 to 5600m 2 A specific ratio of 4800 to 5500m 2 (ii) in terms of/g. In the invention, when the organic monomer is 1,3, 5-tribromobenzene, the specific surface area of the porous aromatic skeleton material is preferably 1000-1500 m 2 (iv)/g, more preferably 1200 to 1500m 2 /g。
In the invention, the porosity/pore volume of the porous aromatic skeleton material is preferably 0.1-5.9 cm 3 g -1 More preferably 1 to 5.9cm 3 g -1 。
The porous aromatic skeleton material prepared by the method has large specific surface area and good hydrothermal stability, and is easy to carry out subsequent sulfonation reaction.
After the porous aromatic skeleton material is obtained, the porous aromatic skeleton material, a sulfonation reagent and a solvent are mixed for sulfonation reaction to obtain the sulfonic group porous aromatic skeleton material.
In the present invention, the sulfonating agent preferably includes chlorosulfonic acid, fuming sulfuric acid or concentrated sulfuric acid, more preferably chlorosulfonic acid. The mass fractions of the concentrated sulfuric acid and the fuming sulfuric acid are not particularly limited in the present invention, and those known in the art may be used.
In the invention, the mass ratio of the porous aromatic skeleton material to the sulfonating agent is preferably 1 (15-20), more preferably 1 (16-19), and most preferably 1 (17-18).
In the present invention, the solvent is preferably dichloromethane, chloroform or nitrobenzene, more preferably dichloromethane. The amount of the solvent used in the present invention is not particularly limited, and any amount of solvent known in the art may be used.
In the present invention, the porous aromatic skeleton material, the sulfonation reagent and the solvent are preferably mixed in a fourth mixing manner to obtain a porous aromatic skeleton material dispersion; and dispersing and cooling the porous aromatic skeleton material, and mixing with a sulfonating agent.
In the present invention, the fourth mixing is more preferably stirring mixing. The stirring and mixing speed in the present invention is not particularly limited, and a stirring speed well known in the art may be used.
In the present invention, the temperature after the cooling is preferably 0 ℃. The cooling method of the present invention is not particularly limited, and a cooling method known in the art may be used; in embodiments of the invention, the cooling is preferably performed in an ice-water bath. In the present invention, the fifth mixing of the porous aromatic skeleton material dispersion liquid and the sulfonating agent is further preferably carried out by dropping the sulfonating agent into the porous aromatic skeleton material dispersion liquid under stirring; the dripping speed is preferably 8-20 mu L/s. In the invention, after the sulfonation reagent is dripped, the obtained mixed system is preferably stirred for 10-30 min, so that the raw materials are mixed more uniformly. The stirring speed in the present invention is not particularly limited, and a stirring speed well known in the art may be used.
In the invention, the temperature of the sulfonation reaction is preferably 10-40 ℃; in the embodiment of the present invention, the sulfonation reaction is preferably performed at room temperature; the sulfonation reaction time is preferably 12-72 hours, more preferably 18-60 hours, and most preferably 24-48 hours. In the invention, sulfonic group-SO is introduced into the molecules of the porous aromatic skeleton material in the sulfonation reaction process 3 H. In the invention, the sulfonation degree of the sulfonic acid group porous aromatic skeleton material is preferably 25-100%. More preferably 50 to 100%.
In the present invention, the formula of the sulfonation reaction is shown in formula (3) and formula (4):
Figure BDA0002364350170000091
after the sulfonation reaction, the system obtained by the sulfonation reaction is preferably washed and then subjected to solid-liquid separation to obtain a solid; and drying the solid to obtain the sulfonic acid group porous aromatic skeleton material. In the present invention, the water washing is preferably ice water washing; the time for washing with ice water in the present invention is not particularly limited, and may be any time known in the art. The solid-liquid separation mode is not particularly limited, and the solid-liquid separation known in the field can be adopted; in the practice of the present invention, the filtration is preferably performed by filtration. The drying mode is not particularly limited in the invention, and the drying mode known in the field can be adopted; in the embodiment of the present invention, the drying manner is preferably vacuum drying; the temperature of the vacuum drying is preferably 90-110 ℃, and more preferably 100 ℃; the vacuum drying time is preferably 2-48 h, and more preferably 12-24 h; the vacuum degree of the vacuum drying in the present invention is not particularly limited, and a vacuum degree of vacuum drying known in the art may be used.
After the sulfonic acid group porous aromatic framework material is obtained, mixing the sulfonic acid group porous aromatic framework material, organic metal salt and a nitrile solvent, and carrying out an ion exchange reaction to obtain a sulfonate porous aromatic framework material; the metal ion in the organic metal salt comprises Ag + Or Cu + 。
In the present invention, the organic metal salt preferably includes silver tetrafluoroborate or copper tetraacetonitrile tetrafluoroborate. The silver tetrafluoroborate or the tetraacetonitrile copper tetrafluoroborate has good stability and is soluble in a nitrile solvent, so that a sufficient amount of monovalent copper source or silver source is provided for the reaction; compared with traditional AgCl and CuCl, silver tetrafluoroborate or tetraacetonitrile copper tetrafluoroborate are not easy to be oxidized and decomposed, thereby providing more convenient conditions for the subsequent ion exchange reaction to be smoothly carried out.
In the invention, the mass ratio of the sulfonic acid group porous aromatic skeleton material to the organic metal salt is preferably 1 (8-12), more preferably 1 (8.5-11.5), and most preferably 1 (9-10).
In the present invention, the nitrile solvent is preferably a mixed solvent of an organic solvent and water; the organic solvent is preferably acetonitrile, phenylacetonitrile, benzonitrile, and more preferably acetonitrile. In the present invention, the volume ratio of the organic solvent to water is preferably 1: (1-10), more preferably 1: (1-5). The invention adopts the mixed solvent of the organic solvent and the water, so that the PAF material and the ionic salt can be better dispersed in the solvent, and the reaction is promoted to be fully carried out.
In the present invention, the sulfonic acid group porous aromatic skeleton material, the organic metal salt and the nitrile solvent are preferably mixed in a sixth mixing manner to obtain a sulfonic acid group porous aromatic skeleton material dispersion; and mixing the sulfonic acid group porous aromatic skeleton material dispersion liquid and an organic metal salt. In the present invention, the concentration of the sulfonic acid group porous aromatic skeleton material dispersion liquid is preferably 0.01 to 1mol/L, and more preferably 0.03 to 0.05 mol/L.
In the present invention, the sixth mixing is more preferably stirring mixing, and the stirring mixing speed in the present invention is not particularly limited, and a stirring speed well known in the art may be used. In the present invention, the time for the first mixing is preferably 5 to 30min, and more preferably 10 to 20 min.
In the present invention, it is further preferable that the sulfonic acid group porous aromatic skeleton material dispersion liquid and the organic metal salt are seventh mixed by adding the organic metal salt to the sulfonic acid group porous aromatic skeleton material dispersion liquid. The addition rate of the organometallic salt is not particularly limited in the present invention, and the addition rate of the organometallic salt known in the art may be used.
In the invention, the temperature of the ion exchange reaction is preferably 10-40 ℃; in the embodiment of the present invention, the ion exchange reaction is preferably performed at room temperature; the time of the ion exchange reaction is preferably 72-144 h, more preferably 80-120 h, and most preferably 84-108 h. In the present invention, Ag is present during the ion exchange reaction + Or Cu + The sulfonic group porous aromatic skeleton material is subjected to-SO 3 H of H is replaced to form sulfonate.
In the present invention, the ion exchange reaction equation is represented by formula (5) and formula (6):
Figure BDA0002364350170000111
after the ion exchange reaction, the invention preferably carries out solid-liquid separation, water washing and drying on the reaction system after the ion exchange in sequence to obtain the sulfonate porous aromatic skeleton material.
The solid-liquid separation mode is not particularly limited, and the solid-liquid separation known in the field can be adopted; in the practice of the present invention, the filtration is preferably performed by filtration. In the invention, the water washing is preferably deionized water washing; the number of washing with water in the present invention is not particularly limited, and may be any number known in the art. In the present invention, the water washing can remove unreacted metal ions adhered to the surface of the sulfonate porous aromatic skeleton material. The drying mode is not particularly limited in the invention, and the drying mode known in the field can be adopted; in the embodiment of the present invention, the drying manner is preferably vacuum drying; the temperature of the vacuum drying is preferably 80-120 ℃, and more preferably 90-110 ℃; the vacuum drying time is preferably 2-72 hours, and more preferably 12-48 hours; the vacuum degree of the vacuum drying in the present invention is not particularly limited, and a vacuum degree of vacuum drying known in the art may be used.
The invention provides a sulfonate porous aromatic skeleton material prepared by the preparation method of the technical scheme, wherein metal ions in sulfonate comprise Ag + Or Cu + 。
In the sulfonate porous aromatic skeleton material provided by the invention, the porous aromatic skeleton material has the advantages of large specific surface area, high porosity, good hydrothermal stability and easiness in post-modification, and can perform ion exchange reaction with monovalent organic copper salt and organic silver salt after sulfonation reactionIntroduction of functional site Cu + Or Ag + And the process of screening a large amount of monomers at the early stage is avoided.
In the invention, the polymerization unit of the sulfonate porous aromatic skeleton material prepared by taking tetrabromotetraphenyl methane as an organic monomer has a structure shown in a formula I, and the polymerization unit of the sulfonate porous aromatic skeleton material prepared by taking 1,3, 5-tribromobenzene as an organic monomer has a structure shown in a formula II:
Figure BDA0002364350170000121
wherein X in formula I and formula II is independently Cu + Or Ag + 。
The invention also provides application of the sulfonate porous aromatic skeleton material as a selective adsorption separating agent of ethylene.
In the present invention, the application preferably includes as a selective adsorbent for ethylene in an ethylene-ethane mixed system.
The invention uses sulfonate porous aromatic skeleton material to selectively adsorb and separate ethylene, because of Cu + And Ag + All have (n-1) d 10 ns 0 In the electronic structure, the s-empty orbit can accept pi electrons in ethylene molecules, the d orbit can feed redundant electrons back to the pi-x orbit of ethylene to form a pi complex, the adsorption effect of the porous aromatic framework material on the ethylene is enhanced through the synergistic effect of sigma-pi (namely pi complexation separation technology), and the selective adsorption on the ethylene is high.
The separation of ethylene-ethane by low-temperature rectification is carried out by condensing each component according to different volatility of ethylene and ethane at low temperature. Compared with the low-temperature distillation technology, the invention takes the sulfonate porous aromatic skeleton material as the selective adsorption separating agent of the ethylene, adopts the pi complex separation technology to separate the ethylene-ethane, does not need to accurately control the temperature during the separation, and can realize the selective adsorption separation of the ethylene-ethane at the room temperature.
The absorption separation method is a method for separating components by utilizing the difference of solubility of the components in an absorbent, and the method is simpler in operation than a low-temperature rectification method, but needs to consume a large amount of solvent. Compared with an absorption separation method, the method takes the sulfonate porous aromatic skeleton material as the selective adsorption separation agent of the ethylene, and a solvent is not required to be additionally added when the pi-complex separation technology is adopted to separate the ethylene from the ethane, so that the cost of the selective adsorption separation of the ethylene is reduced, and the environmental pollution is reduced.
Membrane separation processes utilize the difference in the permeability of ethylene and ethane across a membrane to effect separation. Compared with a membrane separation method, the invention takes the sulfonate porous aromatic skeleton material as the selective adsorption separating agent of ethylene, when the pi complex separation technology is adopted to separate ethylene from ethane, the sulfonate porous aromatic skeleton material obtained by the selective adsorption and desorption of ethylene by the sulfonate porous aromatic skeleton material can also continuously carry out selective adsorption on ethylene, and the repeatability is high.
Therefore, the method for separating the ethylene and the ethane has the advantages of low energy consumption, large adsorption capacity, high separation efficiency, high repeatability and the like.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) 1, 5-cyclooctadiene (cod, 1.05mL, 8.32mmol, CaH) was added under an argon atmosphere 2 Dried), bis (1, 5-cyclooctadiene) nickel (Ni (cod) 2 2.25g, 8.18mmol) and 2,2' -bipyridine (2,2' -Bpy, 1.28g, 8.18mmol) are added into a double-necked bottle, 120mL of anhydrous oxygen-free N, N ' -dimethylformamide is added by a syringe, and the reaction is carried out for 1h at 80 ℃ to obtain an activated catalyst solution; tetrabromo-tetraphenyl methane (1.0g, 1.57mmol) was dissolved in N-N' -dimethylformamide (30mL) to obtain a tetrabromo-tetraphenyl methane solution; adding tetrabromo tetraphenyl methane solution into the activated catalyst solution by using an injector, and reacting for 12 hours at 80 ℃ to obtain purple solution; etc. ofAfter the temperature is reduced to room temperature, 20mL of 6mol/L hydrochloric acid is added into a double-neck bottle, the solution is changed from purple to green, then filtration is carried out to obtain solid, the obtained solid is respectively washed by 6mol/L hydrochloric acid for 2 times, washed by deionized water for 1 time, then respectively subjected to Soxhlet extraction by methanol, acetone, trichloromethane and tetrahydrofuran for 4 hours each time, and vacuum drying is carried out for 48 hours at the temperature of 80 ℃ to obtain the porous aromatic skeleton material (abbreviated as PAF-1, the yield is 97%, and the purity is 99.9%). The carbon nuclear magnetic spectrum of PAF-1 is shown in FIG. 1.
Adding 0.4g of PAF-1 into 100mL of dichloromethane, performing ultrasonic treatment for 15min to obtain a PAF-1 dispersion solution, placing the PAF-1 dispersion solution into an ice water bath, adding 4mL of chlorosulfonic acid, stirring for 10min, then recovering to room temperature, reacting for 72h at the room temperature, filtering the obtained reaction system to obtain a solid, washing the obtained solid with deionized water, and then drying for 24h at-100 kPa and 100 ℃ to obtain the sulfonic acid group porous aromatic skeleton material (abbreviated as PAF-1-SO) 3 H, grey blue solid, 96% yield, 99.8% purity).
2.4g of tetraacetonitrilecontaining tetrafluoroborate was added to 30mL of the mixed solvent (CH) 3 CN:H 2 Dissolving with ultrasonic wave in a volume ratio of 1:1) of O, adding 0.2g of PAF-1-SO 3 H, stirring and reacting for 3 days at room temperature, pouring the obtained reaction system into ice water, filtering to obtain a solid, and washing the obtained solid with acetonitrile and water respectively to obtain the cuprous sulfonate porous aromatic skeleton material (abbreviated as PAF-1-SO) 3 Cu, yield 98%, purity 99.9%).
The reaction was determined by infrared spectroscopy using a Nicolet IS50 infrared spectrometer, KBr pellet assay, to determine whether the reaction occurred and the extent of progress. PAF-1 and PAF-1-SO prepared in this example 3 H and PAF-1-SO 3 The infrared spectrum of Cu is shown in FIG. 2. As can be seen from FIG. 2, PAF-1-SO 3 H、PAF-1-SO 3 Cu is 1085cm -1 、1183cm -1 In the presence of SO 3 - The peak of vibration absorption indicated that the sulfonation reaction occurred smoothly.
The thermal stability of the material was judged by thermogravimetric curves, as determined using a Mettler Toledo, TGA/DSC 3+ thermogravimetric analyzer. Prepared in this examplePAF-1、PAF-1-SO 3 H and PAF-1-SO 3 The thermogravimetric curve of Cu is shown in fig. 3. As can be seen from FIG. 3, PAF-1 begins to lose weight after 420 ℃, and PAF-1-SO 3 H and PAF-1-SO 3 The slow weight loss of Cu after 300 ℃ shows that the PAF-1-SO prepared by the invention is relative to materials such as Metal Organic Frameworks (MOFs) (the weight loss starting temperature is less than or equal to 400℃) 3 Cu has good thermal stability.
Example 2
1.6g of silver tetrafluoroborate was added to 30mL of the mixed solvent (CH) 3 CN:H 2 O volume ratio 1:1), ultrasonic dissolution was performed, and 0.2g of PAF-1-SO prepared in example 1 was added 3 H, stirring and reacting for 72 hours at room temperature, filtering to obtain a solid, washing the obtained solid with acetonitrile and water respectively to obtain the silver sulfonate porous aromatic framework material (abbreviated as PAF-1-SO) 3 Ag, yield 98%, purity 99.7%).
Test example
PAF-1 and PAF-1-SO prepared in example 1 were subjected to the use of an Autosorb iQ2 adsorptometer, Quantachrome Autosorbent apparatus 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 The results of the adsorption isotherm of Ag in the nitrogen adsorption test are shown in FIG. 4. As can be seen from FIG. 4, PAF-1 has a significant adsorption behavior in the low-pressure region, and the specific surface area of PAF-1 can reach 4500m 2 Per g (pore volume 5.9 cm) 3 (g) has an ultra-high specific surface area; PAF-1-SO obtained after sulfonation reaction and ion exchange reaction 3 H、PAF-1-SO 3 Cu and PAF-1-SO 3 The specific surface area of Ag is 1120m 2 /g、812m 2 G and 789m 2 (g), showing that the PAF-1-SO is obtained after functionalization 3 Cu and PAF-1-SO 3 Ag still has a high specific surface area.
PAF-1 and PAF-1-SO prepared in example 1 were subjected to the use of an Autosorb iQ2 adsorptometer, Quantachrome Autosorbent apparatus 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 Ag was tested for ethane and ethylene adsorption capacity at 298K, and the results are shown in fig. 5 and 6. In which fig. 5 is an ethane adsorption curve and fig. 6 is an ethylene adsorption curve. From FIGS. 5 and 6It is known that PAF-1 and PAF-1-SO 3 H、PAF-1-SO 3 Cu and PAF-1-SO 3 The adsorption capacity of Ag to ethane was 65.24cm 3 /g、48.47cm 3 /g、42.31cm 3 G and 44.39cm 3 The adsorption capacity for ethylene is 37.10 cm/g 3 /g、43.90cm 3 /g、91.76cm 3 /g、88.73cm 3 (ii)/g; shows that the PAF-1-SO prepared by the invention 3 Cu and PAF-1-SO 3 The Ag has low ethane adsorption capacity and high ethylene adsorption capacity, and can realize the selective separation of ethylene in an ethylene-ethane mixed system.
PAF-1, PAF-1-SO prepared in example 1 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 The heat of adsorption of Ag to ethylene is shown in FIG. 7. As can be seen from FIG. 7, PAF-1 and PAF-1-SO 3 H、PAF-1-SO 3 Cu and PAF-1-SO 3 The heat of adsorption of Ag on ethylene was 24.16kJ/mol, 27.14kJ/mol, 73.02kJ/mol and 63.30kJ/mol, respectively, indicating that PAF-1-SO prepared by the present invention 3 Cu and PAF-1-SO 3 The selective adsorption performance of Ag on ethylene is good.
PAF-1, PAF-1-SO prepared in example 1 3 H and PAF-1-SO 3 Cu and PAF-1-SO prepared in example 2 3 The change of the adsorption selectivity of Ag to the ethylene-ethane mixed system under the condition of 298K is shown in figure 8. As can be seen from FIG. 8, PAF-1 and PAF-1-SO 3 H、PAF-1-SO 3 Cu、PAF-1-SO 3 The adsorption selectivity of Ag to ethylene in an ethylene-ethane mixed system is respectively 1.12, 1.60, 16.80 and 15.83, which shows that the PAF-1-SO prepared by the invention 3 Cu、PAF-1-SO 3 The Ag has high selective adsorbability to ethylene in an ethylene-ethane mixed system.
Example 3
(1) 1, 5-cyclooctadiene (cod, 1.12mL, 9.216mmol, CaH) was added under an argon atmosphere 2 Dried), bis (1, 5-cyclooctadiene) nickel (Ni (cod) 2 2.52g, 9.216mmol) and 2,2' -bipyridine (2,2' -Bpy, 1.44g, 9.216mmol) were added into a two-necked flask, 120mL of anhydrous oxygen-free N, N ' -dimethylformamide was added by a syringe, and reaction was carried out at 80 ℃ for 1 hour to obtain an activated catalyst solution; 1,3, 5-tribromobenzene (0.804g, 2)56mmol) in N-N' dimethylformamide (30mL) to give a solution of 1,3, 5-tribromobenzene; adding the 1,3, 5-tribromobenzene solution into the activated catalyst solution by using an injector, and reacting for 12h at 80 ℃ to obtain a purple solution; after the temperature is reduced to room temperature, 20mL of 6mol/L hydrochloric acid is added into a double-neck bottle, the solution is changed from purple to green, then filtration is carried out, the obtained solid is respectively washed by the 6mol/L hydrochloric acid for 3 times, washed by deionized water for 1 time, then respectively subjected to Soxhlet extraction by methanol, acetone, chloroform and tetrahydrofuran for 4 hours each time, and vacuum drying is carried out at 80 ℃ for 24 hours, so that the porous aromatic skeleton material (abbreviated as PAF-67, the yield is 95%, and the purity is 99.9%) is obtained. The carbon nuclear magnetic spectrum of PAF-67 is shown in FIG. 9.
Adding 0.4g of PAF-67 into 100mL of dichloromethane, performing ultrasonic treatment for 15min to obtain a PAF-67 dispersion solution, placing the PAF-67 dispersion solution into an ice water bath, adding 4mL of chlorosulfonic acid, stirring for 10min, then recovering to room temperature, reacting for 72h at the room temperature, filtering the obtained reaction system to obtain a solid, washing the obtained solid with deionized water, and then drying for 24h at-100 kPa and 100 ℃ to obtain the sulfonic acid group porous aromatic skeleton material (abbreviated as PAF-67-SO) 3 H, grey blue solid, 97% yield, 99.7% purity).
2.4g of tetraacetonitrilecontaining tetrafluoroborate was added to 30mL of the mixed solvent (CH) 3 CN:H 2 O volume ratio 1:1), ultrasonic dissolving, adding 0.2g PAF-67-SO 3 H, stirring and reacting for 72 hours at room temperature, pouring the obtained reaction system into ice water, filtering to obtain a solid, and washing the obtained solid with acetonitrile and water respectively to obtain the cuprous sulfonate porous aromatic skeleton material (abbreviated as PAF-67-SO) 3 Cu, yield 98%, purity 99.9%).
The reaction was determined by infrared spectroscopy using a Nicolet IS50 infrared spectrometer, KBr pellet assay, to determine whether the reaction occurred and the extent of progress. PAF-67 and PAF-67-SO prepared in this example 3 H and PAF-67-SO 3 The infrared spectrum of Cu is shown in FIG. 10. As can be seen from FIG. 10, PAF-67-SO 3 H、PAF-67-SO 3 Cu at 1096cm -1 、1185cm -1 In the presence of SO 3 - Vibration absorption peak ofIndicating that the sulfonation reaction occurred smoothly.
The thermal stability of the material was judged by thermogravimetric curves, as determined using a Mettler Toledo, TGA/DSC 3+ thermogravimetric analyzer. PAF-67 and PAF-67-SO prepared in this example 3 H and PAF-67-SO 3 The thermogravimetric curve of Cu is shown in fig. 11. As can be seen from FIG. 11, PAF-67 begins to lose weight after 420 ℃, and PAF-67-SO 3 H and PAF-67-SO 3 The slow weight loss of Cu after 300 ℃ shows that the PAF-67-SO prepared by the invention is relative to materials such as Metal Organic Frameworks (MOFs) 3 Cu has good thermal stability.
Example 4
1.6g of silver tetrafluoroborate was added to 30mL of the mixed solvent (CH) 3 CN:H 2 O volume ratio 1:1), dissolved by sonication, and 0.2g of PAF-67-SO prepared in example 3 was added 3 H, stirring and reacting for 72 hours at room temperature, filtering to obtain a solid, washing the obtained solid with acetonitrile and water respectively to obtain the silver sulfonate porous aromatic framework material (abbreviated as PAF-67-SO) 3 Ag, yield 98%, purity 99.9%).
Test example
PAF-67 and PAF-67-SO prepared in example 3 were subjected to the adsorption treatment using an Autosorb iQ2 adsorptometer, a Quantachrome Autoadsorber 3 H and PAF-67-SO 3 Cu and PAF-67-SO prepared in example 4 3 The results of the adsorption isotherm of Ag in the nitrogen adsorption test are shown in FIG. 12. As can be seen from FIG. 12, PAF-67 has a significant adsorption behavior in the low-pressure region, and the specific surface area of PAF-67 can reach 1158.5m 2 Per g (pore volume 1.0 cm) 3 Per gram) having a high specific surface area; PAF-67-SO obtained after sulfonation reaction and ion exchange reaction 3 H、PAF-67-SO 3 Cu and PAF-67-SO 3 The specific surface area of Ag is 850.9m 2 /g、697.6m 2 G and 682m 2 (g), showing that after functionalization, PAF-67-SO is obtained 3 Cu and PAF-67-SO 3 Ag still has a high specific surface area.
PAF-67 and PAF-67-SO prepared in example 3 were subjected to the use of an Autosorb iQ2 adsorptometer, Quantachrome Autosorbent apparatus 3 H and PAF-67-SO 3 Cu and implementationExample 4 preparation of PAF-67-SO 3 Ag was tested for ethane and ethylene adsorption capacity at 298K, and the results are shown in fig. 13 and 14. In which fig. 13 is an ethane adsorption curve and fig. 14 is an ethylene adsorption curve. As can be seen from FIGS. 13 and 14, PAF-67 and PAF-67-SO 3 H、PAF-67-SO 3 Cu and PAF-67-SO 3 The adsorption capacity of Ag to ethane was 67.29cm 3 /g、61.18cm 3 /g、35.12cm 3 G and 40.39cm 3 The adsorption capacity for ethylene is 47.37cm 3 /g、52.41cm 3 /g、97.76cm 3 G and 93.76cm 3 (ii)/g; shows that the PAF-67-SO prepared by the invention 3 Cu and PAF-67-SO 3 The Ag has low ethane adsorption capacity and high ethylene adsorption capacity, and can realize the selective separation of ethylene in an ethylene-ethane mixed system.
PAF-67, PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 Cu and PAF-67-SO prepared in example 4 3 The heat of adsorption of Ag to ethylene is shown in fig. 15. As can be seen from FIG. 15, PAF-67 and PAF-67-SO 3 H、PAF-67-SO 3 Cu and PAF-67-SO 3 The adsorption heat of Ag on ethylene is respectively 30.27kJ/mol, 29.20kJ/mol, 54.14kJ/mol and 48.32kJ/mol, which shows that the PAF-67-SO prepared by the invention 3 Cu and PAF-67-SO 3 The selective adsorption performance of Ag on ethylene is good.
PAF-67, PAF-67-SO prepared in example 3 3 H and PAF-67-SO 3 Cu and PAF-67-SO prepared in example 4 3 The change of the adsorption selectivity of Ag to the ethylene-ethane mixed system under the condition of 298K is shown in FIG. 16. As can be seen from FIG. 16, PAF-67 and PAF-67-SO 3 H、PAF-67-SO 3 Cu、PAF-67-SO 3 The adsorption selectivity of Ag to ethylene-ethane is 1.39, 2.16, 16.56 and 14.04 respectively, which shows that the PAF-67-SO prepared by the invention 3 Cu、PAF-67-SO 3 The selective adsorption of Ag to ethylene in an ethylene-ethane mixed system is high.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (9)

1. The preparation method of the sulfonate porous aromatic skeleton material is characterized by comprising the following steps of:
mixing an organic monomer, a nickel catalyst, a catalyst stabilizer and an anhydrous solvent under a protective atmosphere, carrying out Ullmann reaction, sequentially cooling a reaction system obtained by the Ullmann reaction to room temperature, adjusting the pH value to 0 to-0.78, and carrying out solid-liquid separation to obtain a solid product; washing, Soxhlet extracting and drying the solid product in sequence to obtain a porous aromatic skeleton material; the organic monomer is 1,3, 5-tribromobenzene; the specific surface area of the porous aromatic skeleton material is 1000-5600 m 2 /g；
Mixing the porous aromatic skeleton material, a sulfonation reagent and a solvent, and carrying out sulfonation reaction to obtain a sulfonic group porous aromatic skeleton material;
mixing the sulfonic acid group porous aromatic skeleton material, organic metal salt and a nitrile solvent, and carrying out an ion exchange reaction to obtain a sulfonate porous aromatic skeleton material; the metal ion in the organic metal salt comprises Ag + Or Cu + ；
The temperature of the Ullmann reaction is 80-140 ℃, and the time is 24-72 h;
the organic metal salt comprises silver tetrafluoroborate or copper tetraacetonitrile tetrafluoroborate.
2. The preparation method of claim 1, wherein the nickel catalyst comprises one or more of 1, 5-cyclooctadiene nickel, tetrakis (triphenylphosphine) nickel and bis (triphenylphosphine) nickel bromide;
the catalyst stabilizer includes 2,2' -bipyridine and 1, 5-cyclooctadiene.
3. The method of claim 1 or 2, wherein the molar ratio of the organic monomer to the nickel catalyst to the catalyst stabilizer is 1 (3.5-18) to (3.5-18).
4. The method of claim 1, wherein the sulfonating agent comprises chlorosulfonic acid, oleum, or concentrated sulfuric acid;
the mass ratio of the porous aromatic skeleton material to the sulfonation reagent is 1 (15-20).
5. The preparation method according to claim 1 or 4, wherein the temperature of the sulfonation reaction is 10-40 ℃ and the time is 12-72 hours.
6. The preparation method according to claim 1, wherein the mass ratio of the sulfonic acid group porous aromatic skeleton material to the organic metal salt is 1 (8-12).
7. The preparation method according to claim 1 or 6, wherein the temperature of the ion exchange reaction is 10-40 ℃ and the time is 72-144 h.
8. The sulfonate porous aromatic skeleton material prepared by the preparation method of any one of claims 1 to 7, wherein the metal ion in the sulfonate is Ag + Or Cu + 。
9. Use of the sulfonate porous aromatic matrix material of claim 8 as a selective adsorbent separator for ethylene.
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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101954273A (en) * 2009-07-20 2011-01-26 深圳市普迈达科技有限公司 Organic porous polymer material and synthetic method thereof
CN102504209A (en) * 2011-10-18 2012-06-20 中国科学院长春应用化学研究所 Preparation method of aromatic conjugated polymer
CN103396531A (en) * 2013-07-19 2013-11-20 苏州纳埃净化科技有限公司 Preparation method of porous aromatic skeleton compound
CN104861154A (en) * 2015-04-13 2015-08-26 苏州纳埃净化科技有限公司 Preparation method of porous aromatic framework compound constructed with benzene ring base blocks
CN105199082A (en) * 2015-10-16 2015-12-30 北京化工大学 Method for preparing porous covalent organic material by using ultra-gravity method
CN106750190A (en) * 2016-11-24 2017-05-31 珠海市吉林大学无机合成与制备化学重点实验室 The porous aromatic skeleton compound its preparation method of the high conductivity of thermostable and its application in Proton Exchange Membrane Fuel Cells
CN108610472A (en) * 2018-04-20 2018-10-02 辽宁大学 Nitrogenous porous aromatic skeleton material of one kind and its preparation method and application

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9409116B2 (en) * 2012-06-04 2016-08-09 The Texas A&M University System Porous polymer network materials

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101954273A (en) * 2009-07-20 2011-01-26 深圳市普迈达科技有限公司 Organic porous polymer material and synthetic method thereof
CN102504209A (en) * 2011-10-18 2012-06-20 中国科学院长春应用化学研究所 Preparation method of aromatic conjugated polymer
CN103396531A (en) * 2013-07-19 2013-11-20 苏州纳埃净化科技有限公司 Preparation method of porous aromatic skeleton compound
CN104861154A (en) * 2015-04-13 2015-08-26 苏州纳埃净化科技有限公司 Preparation method of porous aromatic framework compound constructed with benzene ring base blocks
CN105199082A (en) * 2015-10-16 2015-12-30 北京化工大学 Method for preparing porous covalent organic material by using ultra-gravity method
CN106750190A (en) * 2016-11-24 2017-05-31 珠海市吉林大学无机合成与制备化学重点实验室 The porous aromatic skeleton compound its preparation method of the high conductivity of thermostable and its application in Proton Exchange Membrane Fuel Cells
CN108610472A (en) * 2018-04-20 2018-10-02 辽宁大学 Nitrogenous porous aromatic skeleton material of one kind and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Baiyan Li, et al..Introduction of π‑Complexation into Porous Aromatic Framework for Highly Selective Adsorption of Ethylene over Ethane.《J. Am. Chem. Soc.》.2014,第8654-8660页. *
Introduction of π‑Complexation into Porous Aromatic Framework for Highly Selective Adsorption of Ethylene over Ethane;Baiyan Li, et al.;《J. Am. Chem. Soc.》;20140605;第8654-8660页 *

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