CN106378109B - A kind of porous polycarbazole polymer and its preparation method and application - Google Patents
A kind of porous polycarbazole polymer and its preparation method and application Download PDFInfo
- Publication number
- CN106378109B CN106378109B CN201610883474.4A CN201610883474A CN106378109B CN 106378109 B CN106378109 B CN 106378109B CN 201610883474 A CN201610883474 A CN 201610883474A CN 106378109 B CN106378109 B CN 106378109B
- Authority
- CN
- China
- Prior art keywords
- polymer
- polycarbazole
- porous
- crosslinking agent
- carbazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
- B01J20/267—Cross-linked polymers
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28066—Surface area, e.g. B.E.T specific surface area being more than 1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Nanotechnology (AREA)
- Polyesters Or Polycarbonates (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention discloses a kind of porous polycarbazole polymer and its preparation method and application.1) preparation method of porous polycarbazole polymer of the invention is the following steps are included: prepare more carbazole substituted pyridine compounds；2) above-mentioned more carbazole substituted pyridine compounds are dissolved in organic solvent, prepare the organic solvent solution of more carbazole substituted pyridine compounds；3) into the organic solvent solution of above-mentioned more carbazole substituted pyridines, addition is dissolved in Lewis acid catalyst and crosslinking agent is formed by mixed solution reaction, and the Lewis hydrochlorate of porous polycarbazole is made in then washed, filtering, drying；4) the Lewis hydrochlorate of above-mentioned porous polycarbazole is adjusted pH with aqueous slkali is alkalinity, and porous polycarbazole polymer is made in washing, filtering, drying.Porous material large specific surface area of the invention, stability are good, and gas absorption power is strong, acid-fast alkali-proof, especially in CO2Absorption aspect superior performance.
Description
Technical field
The present invention relates to a kind of polycarbazole polymer, and in particular to a kind of porous polycarbazole, preparation method and in CO2It inhales
The application in subsidiary formula face.
Background technique
Porous material contains a certain number of holes, specific surface area with higher, light-weight, good penetrability.By aperture
Size is divided into poromerics (aperture is less than 2nm), mesoporous material (aperture 2-50nm), large pore material (aperture is greater than 50nm).It is more
The photoelectric properties of Porous materials, permeance property, absorption property attract attention.
Connect mode according to the element of porous material composition and key, porous material is divided into inorganic, inorganic-organic hybridization, organic
Porous material.Compared to inorganic, inorganic-organic hybridization porous material, the monomer of organic porous material is rich and varied, leads between monomer
Covalently key connection is crossed, it is excellent to have that skeleton composition is abundant, modified is strong, stability is good, specific surface area is high, cellular structure is adjustable etc.
Point, gas storage with separate, be catalyzed, sense and in terms of have potential application.
In recent years, the research of Porous-Organic polycarbazole material becomes a hot spot in organic porous material field.Carbazole
All more stable to heat, bronsted lowry acids and bases bronsted lowry as a kind of critically important nitrogen-containing heterocycle compound, polycarbazole has stiff backbone and conjugation
Electron rich system not only improves to form permanent porous material, and can enhance the interaction between absorbate and adsorbent,
It is greatly improved the adsorption capacity to sour gas such as carbon dioxide containing N structure.
Summary of the invention
According to the first embodiment of the present invention, it is poly- to provide a kind of porous polycarbazole with structural unit I by the present invention
Close object:
Generally, the average pore size of above-described porosity polycarbazole polymer or its mesylate is 1.5-25nm, excellent
Select 1.6-20nm, preferably 1.8-15nm, preferably 2-10nm.
It is preferred that its specific surface area is 600-1200cm2/ g, preferably 700-1000cm2/ g, more preferable 800-900cm2/g。
In general, above-mentioned porosity polycarbazole polymer is existed by more carbazole substituted pyridine compounds and crosslinking agent
It carries out reacting cross-linked polymer obtained in the presence of Lewis acid catalyst；Preferably, the crosslinking agent is selected from diformazan
One of oxygroup methane, dichloropropane, dichloroethanes, methylene chloride, Bromofume or methylene bromide are a variety of, and preferably two
Methoxyl group methane.
The mesylate of above-described polymer has following structure unit II:
According to the second embodiment of the present invention, the present invention also provides the preparation method of above-mentioned polymer, including it is following
Step:
1) more carbazole substituted pyridine compounds are prepared；
2) above-mentioned more carbazole substituted pyridine compounds are dissolved in organic solvent, prepare having for more carbazole substituted pyridine compounds
Solvent solution；
3) it into the organic solvent solution of above-mentioned more carbazole substituted pyridine compounds, adds by Lewis acid catalyst and friendship
Connection agent is formed by mixed solution and is reacted, and the Lewis hydrochlorate of porous polycarbazole is made in then washed, filtering, drying；
4) the Lewis hydrochlorate of above-mentioned porous polycarbazole is adjusted pH with aqueous slkali is alkalinity, and washing, filtering, drying are made
The structural unit is the porous polycarbazole polymer of I.
The present invention has no particular/special requirement to the preparation method of more carbazole substituted pyridine compounds, using the conventional prior art
Synthesis.For example, the method that nucleophilic displacement of fluorine may be selected.
The present invention has the porous polycarbazole polymer of structural unit I, and structure can be as follows:
Preparation method of the invention, in step 2), organic solvent is selected from chloroform, methylene chloride, dichloroethanes
Or one of carbon tetrachloride or a variety of, preferably dichloroethanes.
Preparation method of the invention, in step 2), the organic solvent solution concentration of more carbazole substituted pyridine compounds is
0.010-0.020mmol/ml.It is preferred that 0.012-0.016mmol/ml.Such as 0.015mmol/ml.
Preparation method of the invention in step 3), is preferably reacted under inert atmosphere protection, inert atmosphere is selected from
Nitrogen atmosphere, helium atmosphere or argon atmosphere, preferably nitrogen atmosphere.
Preparation method of the invention, in step 3), Lewis acid catalyst selected from aluminium chloride, iron chloride, boron trifluoride or
Methanesulfonic acid, preferably methanesulfonic acid.
Preparation method of the invention, in step 3), crosslinking agent is selected from dimethoxymethane, dichloropropane, two chloroethenes
One of alkane, methylene chloride, Bromofume or methylene bromide are a variety of, preferably dimethoxymethane.
The phenyl ring of carbazole has a higher cloud density similar to biphenyl, the benzene ring structure of diphenylamines, between carbazole group
The position 3,6- can react.Under the catalysis of Lewis acid, self-condensation reaction can occur, generate porous material.
Methanesulfonic acid is catalyzed to obtain poromeric gas absorption as a kind of stronger Lewis acid catalyst of acidity
Performance will be got well compared with what iron chloride, aluminium chloride, boron trifluoride were catalyzed.This is related with methanesulfonic acid catalytic activity itself, secondly
There is a substantial connection with its structure, two carbazole pyridines and acid strong Lewis acid catalyst and contain metal easily at porous polymer salt
Lewis acid catalyst easily form Porous coordination polymer.
In view of the structure and chemical property of more carbazole substituted pyridines, Lewis acid catalyst and dimethoxymethane are utilized
The collective effect of equal crosslinking agents, occurs Friedel-Crafts alkylated reaction, prepares the porous polycarbazole polymer of super crosslinking
Material.Lewis acid catalyst is catalyzed the generation of the Friedel-Crafts alkylated reaction between carbazoles monomer and crosslinking agent.
Preparation method of the invention, in step 3), in the organic solution of more carbazole substituted pyridines, addition is dissolved in Lewis acid
Catalyst and crosslinking agent are formed by mixed solution, are first stirred to react under 30-60 DEG C (preferably 40-45 DEG C), when being stirred to react
Between 2-10h, preferably 4-8h.It then heats under 60-90 DEG C (preferably 75-80 DEG C) and reacts, reaction time 15-30h, preferably 19-
24h。
Preparation method of the invention, in step 3), more carbazole substituted pyridines: crosslinking agent: the molar ratio of Lewis acid is 1:2-
6:8-16.It is preferred that 1:3-5:12-16.More preferable 1:4:14.
Preparation method of the invention, in step 4), aqueous slkali optionally from sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide,
It is preferred that sodium hydroxide solution.
The present invention also provides the mesylate II of above-mentioned polymer:
The present invention also provides the preparation methods of the mesylate of above-mentioned polymer, that is, only includes above according to the present invention
Second embodiment preparation method in and 3) step 1), 2), that is to say, that the system of the mesylate of above-mentioned polymer
Preparation Method the following steps are included:
1) more carbazole substituted pyridine compounds are prepared；
2) above-mentioned more carbazole substituted pyridine compounds are dissolved in organic solvent, prepare having for more carbazole substituted pyridine compounds
Solvent solution；
3) it into the organic solvent solution of above-mentioned more carbazole substituted pyridine compounds, adds by methanesulfonic acid catalyzed agent and crosslinking
Agent is formed by mixed solution reaction, and the porous polycarbazole with structural unit II is made in then washed, filtering, drying
Mesylate.
Step 1) here, 2) and 3) in various optimum conditions it is as previously discussed.
More specifically, the present invention also provides the preparation method of the mesylate of above-mentioned polymer, include the following steps:
1) bis- carbazole pyridine of 2,5- is prepared；
2) 2,5-, bis- carbazole pyridine is dissolved in organic solvent, prepares the organic solvent solution of 2,5-, bis- carbazole pyridine；It is preferred that
, organic solvent is optionally from chloroform, methylene chloride, dichloroethanes, carbon tetrachloride, more preferable dichloroethanes；It is preferred that 2,
The organic solvent solution concentration of bis- carbazole pyridine of 5- be 0.010-0.020mmol/ml, more preferable 0.012-0.016mmol/ml,
Such as 0.015mmol/ml；
3) into the organic solution of above-mentioned 2,5-, bis- carbazole pyridine, addition is dissolved in methanesulfonic acid and crosslinking agent is formed by mixing
Solution reaction (is preferably reacted under inert atmosphere protection, preferably nitrogen atmosphere, helium atmosphere, argon atmosphere, more preferable nitrogen
Gas atmosphere), the mesylate II of porous polycarbazole is made in then washed, filtering, drying；Preferably, crosslinking agent selection two
Methoxyl group methane, dichloropropane, dichloroethanes, methylene chloride, Bromofume, methylene bromide, more preferable dimethoxymethane.
The synthetic method of the prior art can be used in 2,5- bis- carbazole pyridines, the method for such as using nucleophilic displacement of fluorine, step packet
It includes: potassium carbonate, cuprous iodide, 18- crown ether -6 and n,N-dimethylacetamide being added in round-bottomed flask, adds 2,5- dibromo
Pyridine.Stirring at normal temperature 30min under nitrogen protection is heated to 165 DEG C, and the carbazole for being dissolved in n,N-dimethylacetamide is added,
72h is reacted, system is down to room temperature after reaction.Water is added and stirs 30min, is extracted with ethyl acetate, uses anhydrous magnesium sulfate
Dry organic layer, the solid rotated are isolated with pillar layer separation (petroleum ether: the volume ratio of methylene chloride is 5:1)
Yellow solid product, i.e. bis- carbazole pyridine of 2.5-.(bibliography He-ping Shi et al, Aggregation induced
ratiometric fluorescence change for a novel boron-based carbazole derivative
Chem.Commun.,2012,48,8586–8588)
The mesylate II of the porous polycarbazole polymer of the present invention, structure can be as follows:
The preparation method of mesylate of the present invention, in step 3), in the organic solution of 2,5- bis- carbazole pyridines, addition is dissolved in
Methanesulfonic acid and crosslinking agent are formed by mixed solution, are first stirred to react under 30-60 DEG C (preferably 40-45 DEG C), when being stirred to react
Between 2-10h, preferably 4-8h；It then heats under 60-90 DEG C (preferably 75-80 DEG C) and reacts, reaction time 15-30h, preferably 19-
24h。
The preparation method of mesylate of the present invention, in step 3), 2,5- bis- carbazole pyridines: crosslinking agent: mole of methanesulfonic acid
Than for 1:2-6:8-16.It is preferred that 1:3-5:12-16.More preferable 1:4:14.
The mesylate II of the porous polycarbazole polymer of the present invention, wherein the introducing of sulfonic acid group substantially increases titanium dioxide
Carbon adsorption performance, the binding site of carbon dioxide can be increased by furthermore introducing N, additionally due to S has electron delocalization in sulfonic acid group
P track, greatly reduce the alkalinity of pyridine and carbazole N, therefore do not have between the N on carbon dioxide and pyridine and carbazole
Chemical interaction.
P-methyl benzenesulfonic acid does acidic catalyst, while pyridine p-toluenesulfonic acid can also do mild acidic catalyst, add
Entering can first after methanesulfonic acid and pyridine is at salt (i.e. pyridine mesylate), and then the pyridine mesylate plays mild acidic catalyst work
With wherein pyridine works as a buffer.
The present invention also provides porous polycarbazole polymer of the invention or preparation method according to the present invention prepare it is more
The mesylate of the porous material of hole polycarbazole polymer and porous polycarbazole polymer of the invention, preparation method system
The porous material of standby porous polycarbazole polymer mesylate, the aperture of the porous material are 1.5-25nm, preferably 1.6-
20nm, preferably 1.8-15nm, preferably 2-10nm.Preferably, the specific surface area of porous material is 600-1200cm2/ g, preferably
700-1000cm2/ g, more preferable 800-900cm2/g。
The present invention also provides porous polycarbazole polymer of the invention or preparation method according to the present invention prepare it is more
The mesylate of hole polycarbazole polymer and porous polycarbazole polymer of the invention, the porous of preparation method preparation gather
Carbazole polymer mesylate, the application in the separation of chemical catalysis, gas absorption or molecule.Such as it is right in gas absorption
CO2Capture and isolated application.
Present invention polymer obtained is cross-linked polymer, can not Accurate Determining its molecular weight.Physical aspect can be
Powder or solid.
In the present invention, the preparation of more carbazole substituted pyridine compounds and 2, bis- carbazole pyridine of 5- is universal using the prior art
Scheme.
Porous polycarbazole polymer prepared by the present invention, to CO in gas absorption2Capture and separate using upper
With advantage, for experimental result, the carbon dioxide adsorption of existing two carbazoles benzene porous polymer CPOP-2 is up to 7.8%
(i.e. 1.77mmol/g) 273K, 1bar (can refer to document small 2014,10, No.2,308-315), and two that we synthesize
The carbon dioxide adsorption of carbazole pyridine porous polymer II is up to 12.3% (i.e. 2.79mmol/g) 273K, 1bar.Adsorbance mentions
It rises clearly.Compared with prior art, porous polycarbazole polymer of the invention has the advantages that
1) porous material large specific surface area of the invention, stability are good, and carbazole is as a kind of critically important nitrogen-containing hetero cyclisation
Object is closed, all more stable to heat, bronsted lowry acids and bases bronsted lowry, polycarbazole has stiff backbone and conjugation electron rich system, is conducive to be formed permanent
Porous material, and the interaction between absorbate and adsorbent can be enhanced.
2) porous material of the invention, gas absorption power is strong, acid-fast alkali-proof, especially in CO2Absorption aspect superior performance.Knot
Structure unit is the porous polycarbazole polymer of I, under the conditions of 298K, CO2Adsorptive value up to 1.75mmol/g (1bar).It is porous
The mesylate II of polycarbazole polymer, under the conditions of 298K, CO2Adsorptive value up to 2.10mmol/g (1bar), in 273K
Under the conditions of, CO2Adsorptive value up to 3.96mmol/g (800mmHg).
Detailed description of the invention
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of structural unit I；
Fig. 2 is the mesylate II (Cz-HCP-I) of the porous polycarbazole polymer of embodiment 1 to carbon dioxide adsorption
Isothermal curve figure (298K)；
Fig. 3 is the mesylate II (Cz-HCP-I) of the porous polycarbazole polymer of embodiment 1 to carbon dioxide adsorption
Isothermal curve figure (273K)；
Fig. 4 be 2 structural unit of embodiment be I porous polycarbazole polymer (Cz-HCP-II) to carbon dioxide adsorption
Isothermal curve figure (298K)；
Fig. 5 is the pore-size distribution of the mesylate II (Cz-HCP-I) of the porous polycarbazole polymer of embodiment 1；
Fig. 6 be the nitrogen of the mesylate II (Cz-HCP-I) of the porous polycarbazole polymer of embodiment 1 inhale-isothermal is desorbed
Curve graph；
Fig. 7 is the mesylate II (Cz-HCP-I) of the porous polycarbazole polymer of embodiment 1 and the structure list of embodiment 2
Member is the infared spectrum of the porous polycarbazole polymer (Cz-HCP-II) of I.
Specific embodiment
The present invention provides a kind of porous polycarbazole polymer that structural unit is I:
The present invention also provides the preparation methods of above-mentioned polymer, comprising the following steps:
1) more carbazole substituted pyridine compounds are prepared；
2) above-mentioned more carbazole substituted pyridine compounds are dissolved in organic solvent, prepare having for more carbazole substituted pyridine compounds
Solvent solution；
3) into the organic solvent solution of above-mentioned more carbazole substituted pyridines, addition is dissolved in Lewis acid catalyst and crosslinking agent
It is formed by mixed solution reaction, the Lewis hydrochlorate of porous polycarbazole is made in then washed, filtering, drying；
4) the Lewis hydrochlorate of above-mentioned porous polycarbazole is adjusted pH with aqueous slkali is alkalinity, and washing, filtering, drying are made
The structural unit is the porous polycarbazole polymer of I.
Preparation method of the invention, in step 2), organic solvent is optionally from chloroform, methylene chloride, dichloroethanes, four
Chlorination carbon, preferably dichloroethanes.
Preparation method of the invention, in step 2), the organic solvent solution concentration of more carbazole substituted pyridine compounds is
0.010-0.020mmol/ml.It is preferred that 0.012-0.016mmol/ml.Such as 0.015mmol/ml.
Preparation method of the invention in step 3), is preferably reacted under inert atmosphere protection, inert atmosphere optionally from
Nitrogen atmosphere, helium atmosphere, argon atmosphere, preferably nitrogen atmosphere.
Preparation method of the invention, in step 3), Lewis acid catalyst optionally from aluminium chloride, iron chloride, boron trifluoride,
Methanesulfonic acid, preferably methanesulfonic acid.
Preparation method of the invention, in step 3), crosslinking agent optionally from dimethoxymethane, dichloropropane, dichloroethanes,
Methylene chloride, Bromofume, methylene bromide, preferably dimethoxymethane.
Preparation method of the invention, in step 3), in the organic solution of more carbazole substituted pyridines, addition is dissolved in Lewis acid
Catalyst and crosslinking agent are formed by mixed solution, are first stirred to react under 30-60 DEG C (preferably 40-45 DEG C), when being stirred to react
Between 2-10h, preferably 4-8h.It then heats under 60-90 DEG C (preferably 75-80 DEG C) and reacts, reaction time 15-30h, preferably 19-
24h。
Preparation method of the invention, in step 3), more carbazole substituted pyridines: crosslinking agent: the molar ratio of Lewis acid is 1:2-
6:8-16.It is preferred that 1:3-5:12-16.More preferable 1:4:14.
Preparation method of the invention, in step 4), aqueous slkali optionally from sodium hydroxide solution, potassium hydroxide solution, ammonium hydroxide,
It is preferred that sodium hydroxide solution.
The present invention also provides the mesylate II of above-mentioned polymer:
The present invention also provides the preparation methods of the mesylate of above-mentioned polymer, include the following steps:
1) bis- carbazole pyridine of 2,5- is prepared；
2) 2,5-, bis- carbazole pyridine is dissolved in organic solvent, prepares the organic solvent solution of 2,5-, bis- carbazole pyridine；It is preferred that
, organic solvent is optionally from chloroform, methylene chloride, dichloroethanes, carbon tetrachloride, more preferable dichloroethanes；It is preferred that 2,
The organic solvent solution concentration of bis- carbazole pyridine of 5- be 0.010-0.020mmol/ml, more preferable 0.012-0.016mmol/ml,
Such as 0.015mmol/ml；
3) into the organic solution of above-mentioned 2,5-, bis- carbazole pyridine, addition is dissolved in methanesulfonic acid and crosslinking agent is formed by mixing
Solution reaction (is preferably reacted under inert atmosphere protection, preferably nitrogen atmosphere, helium atmosphere, argon atmosphere, more preferable nitrogen
Gas atmosphere), the mesylate II of porous polycarbazole is made in then washed, filtering, drying；Preferably, crosslinking agent selection two
Methoxyl group methane, dichloropropane, dichloroethanes, methylene chloride, Bromofume, methylene bromide, more preferable dimethoxymethane.
The preparation method of mesylate of the present invention, in step 3), in the organic solution of 2,5- bis- carbazole pyridines, addition is dissolved in
Methanesulfonic acid and crosslinking agent are formed by mixed solution, are first stirred to react under 30-60 DEG C (preferably 40-45 DEG C), when being stirred to react
Between 2-10h, preferably 4-8h；It then heats under 60-90 DEG C (preferably 75-80 DEG C) and reacts, reaction time 15-30h, preferably 19-
24h。
The preparation method of mesylate of the present invention, in step 3), 2,5- bis- carbazole pyridines: crosslinking agent: mole of methanesulfonic acid
Than for 1:2-6:8-16.It is preferred that 1:3-5:12-16.More preferable 1:4:14.
The present invention also provides porous polycarbazole polymer of the invention or preparation method according to the present invention prepare it is more
The mesylate of the porous material of hole polycarbazole polymer and porous polycarbazole polymer of the invention, preparation method system
The porous material of standby porous polycarbazole polymer mesylate, the aperture of the porous material are 2-10nm.Preferably, porous
The specific surface area of material is 600-1200cm2/g。
The present invention also provides porous polycarbazole polymer of the invention or preparation method according to the present invention prepare it is more
The mesylate of hole polycarbazole polymer and porous polycarbazole polymer of the invention, the porous of preparation method preparation gather
Carbazole polymer mesylate, the application in the separation of chemical catalysis, gas absorption or molecule.Such as it is right in gas absorption
CO2Capture and isolated application.
The mesylate II of the porous polycarbazole polymer of embodiment 1, the preparation that structural unit is the porous polycarbazole polymer of I
In the there-necked flask of 50mL, 2,5-, bis- carbazole pyridine 81.8mg (0.2mmol), FDA 60.8mg is added
(0.8mmol) and dry dichloroethanes is added methanesulfonic acid 268.8mg (2.8mmol) and is used as Lewis acid catalyst, in nitrogen
It is heated to 45 DEG C of reaction 5h under protection, is then warming up to 80 DEG C of reaction 19h again, obtains dark green solid, wash removing with methanol
Remaining catalyst and the complete monomer of unreacted, are then mentioned for 24 hours with methanol rope, dry, are obtained bright yellow solid powder 62mg, that is, are made
Obtain the mesylate II of the porous polycarbazole polymer.
It is alkalinity that the mesylate II of porous polycarbazole polymer, which is adjusted pH with the sodium hydroxide solution of concentration 1M, is washed
It washs, filters, vacuum oven is dry, and it is the porous polycarbazole polymer of I that structural unit, which is made,.
Above-mentioned product is detected using hydrogen nuclear magnetic resonance spectrometer, it is total using the AV-400 nuclear-magnetism of Bruker company of the U.S.
Vibration Meter, deuterated chloroform (CDC13) are the deuterated reagent of sample, and tetramethylsilane (TMS) is internal standard.Gained nucleus magnetic hydrogen spectrum figure is shown in figure
1。
Using the first for the porous polycarbazole polymer that full-automatic specific surface area and lacunarity analysis instrument prepare embodiment 1
Sulfonate II is detected, using the Tristar II 3020 of Micromeritics company of the U.S..150 DEG C of degassing conditions,
24h.Measuring its BET specific surface area is 899m2/ g, according to non-localized density functional theory calculated hole diameters 4.77nm.
The structural unit for using full-automatic specific surface area and lacunarity analysis instrument to prepare embodiment 1 is the porous poly- click of I
The mesylate II of azoles polymer and porous polycarbazole polymer is detected, using Micromeritics company of the U.S.
Tristar II 3020.150 DEG C of degassing conditions, for 24 hours.Measuring its structural unit is the porous polycarbazole polymer of I, in 298K and
Carbon dioxide adsorption is 1.75mmol/g under the conditions of 1bar.The mesylate II for measuring its porous polycarbazole polymer,
Carbon dioxide adsorption is 2.10mmol/g under the conditions of 298K and 1bar；Carbon dioxide adsorption under the conditions of 273K and 800mmHg
Amount is 3.96mmol/g.
Embodiment 2
Embodiment 1 is repeated, is only heated to 40 DEG C of reaction 8h under nitrogen protection, is then warming up to 75 DEG C of reactions again for 24 hours.
Embodiment 3
Embodiment 1 is repeated, 2,5-, bis- carbazole pyridine 122.7mg (0.3mmol), FDA 114.0mg is only added
(1.5mmol) and dry dichloroethanes, is added methanesulfonic acid 432.0mg (4.5mmol)
According to the detection device and condition in embodiment 1, to the first of porous polycarbazole polymer prepared by embodiment 1-3
Sulfonate II, every detection data that structural unit is the porous polycarbazole polymer of I are as follows:
In the present invention, the more carbazole substituted pyridines of nitrogenous compound and methanesulfonic acid are at the porous polymer after salt, than not saliferous
Nitrogenous porous polymer in CO2The performance for adsorbing aspect is more superior.
Claims (21)
1. a kind of porosity polycarbazole polymer with structural unit I:
2. porosity polycarbazole polymer according to claim 1, wherein the average pore size of the polymer is 1.5-25nm；
And/or the specific surface area of the polymer is 600-1200cm2/g。
3. porosity polycarbazole polymer according to claim 2, wherein the average pore size of the polymer is 1.6-20nm；
And/or the specific surface area of the polymer is 700-1000cm2/g。
4. porosity polycarbazole polymer according to claim 3, wherein the average pore size of the polymer is 1.8-15nm；
And/or the specific surface area of the polymer is 800-900cm2/g。
5. porosity polycarbazole polymer described in any one of -4 according to claim 1, wherein porosity polycarbazole polymer
It is to be carried out reacting cross-linked polymeric obtained in the presence of Lewis acid catalyst with crosslinking agent by more carbazole substituted pyridine compounds
Object.
6. porosity polycarbazole polymer according to claim 5, in which: the crosslinking agent is selected from dimethoxy first
One of alkane, dichloropropane, dichloroethanes, methylene chloride, Bromofume or methylene bromide are a variety of.
7. porosity polycarbazole polymer according to claim 6, in which: the crosslinking agent is dimethoxymethane.
8. according to claim 1-4, porosity polycarbazole polymer described in any one of 6-7, the wherein first of the polymer
Sulfonate has following structure unit II:
9. porosity polycarbazole polymer according to claim 5, wherein the mesylate of the polymer has following knot
Structure unit II:
10. the method for preparing polymer described in any one of claim 1-9, which is characterized in that this method includes following
Step:
1) more carbazole substituted pyridine compounds are prepared；
2) above-mentioned more carbazole substituted pyridine compounds are dissolved in organic solvent, prepare the organic molten of more carbazole substituted pyridine compounds
Agent solution；
3) it into the organic solvent solution of above-mentioned more carbazole substituted pyridine compounds, adds by Lewis acid catalyst and crosslinking agent
It is formed by mixed solution to be reacted, the Lewis hydrochlorate of porous polycarbazole is made in then washed, filtering, drying；
4) the Lewis hydrochlorate of above-mentioned porous polycarbazole is adjusted pH with aqueous slkali is alkalinity, and washing, filtering, drying, being made has
The porous polycarbazole polymer of the structural unit I.
11. according to the method described in claim 10, it is characterized in that, in step 2), organic solvent be selected from chloroform,
One of methylene chloride, dichloroethanes or carbon tetrachloride are a variety of；
And/or
In step 2), the organic solvent solution concentration of more carbazole substituted pyridine compounds is 0.010-0.020mmol/ml.
12. according to the method for claim 11, which is characterized in that in step 2), organic solvent is dichloroethanes；
And/or
In step 2), the organic solvent solution concentration of more carbazole substituted pyridine compounds is 0.012-0.016mmol/ml.
13. method described in any one of 0-12 according to claim 1, which is characterized in that in step 3), in inert atmosphere protection
Under reacted；
And/or
Lewis acid catalyst is selected from aluminium chloride, iron chloride, boron trifluoride or methanesulfonic acid；
And/or
Crosslinking agent is selected from dimethoxymethane, dichloropropane, dichloroethanes, methylene chloride, Bromofume or methylene bromide
One of or it is a variety of.
14. according to the method for claim 13, it is characterised in that: inert atmosphere is selected from helium atmosphere or argon atmosphere；
And/or
Lewis acid catalyst is methanesulfonic acid；
And/or
Crosslinking agent is dimethoxymethane.
15. method described in any one of 0-12,14 according to claim 1, which is characterized in that in step 3), more carbazoles replace
In the organic solution of pyridine, addition is dissolved in Lewis acid catalyst and crosslinking agent is formed by mixed solution, first at 30-60 DEG C
It is stirred to react, is stirred to react time 2-10h；It then heats at 60-90 DEG C and is stirred to react, reaction time 15-30h；
And/or
In step 3), more carbazole substituted pyridines: crosslinking agent: the molar ratio of Lewis acid is 1:2-6:8-16.
16. according to the method for claim 13, which is characterized in that in step 3), the organic solution of more carbazole substituted pyridines
In, addition is dissolved in Lewis acid catalyst and crosslinking agent is formed by mixed solution, is first stirred to react at 30-60 DEG C, stirring is anti-
2-10h between seasonable；It then heats at 60-90 DEG C and is stirred to react, reaction time 15-30h；
And/or
In step 3), more carbazole substituted pyridines: crosslinking agent: the molar ratio of Lewis acid is 1:2-6:8-16.
17. according to the method for claim 15, which is characterized in that step 3) is first stirred to react at 40-45 DEG C, and stirring is anti-
4-8h between seasonable；It then heats at 75-80 DEG C and is stirred to react, reaction time 19-24h；
And/or
In step 3), more carbazole substituted pyridines: crosslinking agent: the molar ratio of Lewis acid is 1:3-5:12-16.
18. according to the method for claim 16, which is characterized in that step 3) is first stirred to react at 40-45 DEG C, and stirring is anti-
4-8h between seasonable；It then heats at 75-80 DEG C and is stirred to react, reaction time 19-24h；
And/or
In step 3), more carbazole substituted pyridines: crosslinking agent: the molar ratio of Lewis acid is 1:3-5:12-16.
19. the method for preparing the mesylate of the polymer according to claim 8 or 9, which is characterized in that this method includes
Following steps:
1) more carbazole substituted pyridine compounds are prepared；
2) above-mentioned more carbazole substituted pyridine compounds are dissolved in organic solvent, prepare the organic molten of more carbazole substituted pyridine compounds
Agent solution；
3) it into the organic solvent solution of above-mentioned more carbazole substituted pyridine compounds, adds by methanesulfonic acid catalyzed agent and crosslinking agent institute
The mixed solution of formation reacts, then washed, filtering, dry, the methylsulphur of the obtained porous polycarbazole with structural unit II
Hydrochlorate.
20. the purposes of porosity polycarbazole polymer described in any one of -9 according to claim 1, wherein the polymer is answered
For in the separation of chemical catalysis, gas absorption or molecule.
21. the purposes of porosity polycarbazole polymer according to claim 20, wherein the polymer is inhaled applied to gas
Attached middle school is to CO2Capture with separate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610883474.4A CN106378109B (en) | 2016-10-10 | 2016-10-10 | A kind of porous polycarbazole polymer and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610883474.4A CN106378109B (en) | 2016-10-10 | 2016-10-10 | A kind of porous polycarbazole polymer and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106378109A CN106378109A (en) | 2017-02-08 |
| CN106378109B true CN106378109B (en) | 2019-02-12 |
Family
ID=57937199
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610883474.4A Expired - Fee Related CN106378109B (en) | 2016-10-10 | 2016-10-10 | A kind of porous polycarbazole polymer and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106378109B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108586713A (en) * | 2018-05-17 | 2018-09-28 | 湘潭大学 | A kind of tetrazine ring polycarbazole and its preparation method and application |
| CN108822294B (en) * | 2018-07-09 | 2020-12-01 | 国家纳米科学中心 | Polypyridyl polycarbazole polymer and preparation method and application thereof |
| CN109293900B (en) * | 2018-09-30 | 2021-02-12 | 河北科技大学 | Process for the preparation of microporous polymers for gas storage |
| CN112164789B (en) * | 2019-11-04 | 2022-02-22 | 多氟多新材料股份有限公司 | Application of triazine-carbazole polymer in organic electrode material |
| CN111154077A (en) * | 2020-01-16 | 2020-05-15 | 湘潭大学 | Tetrazine cyclo poly diphenyl indole, preparation method and application thereof |
| CN112812356B (en) * | 2020-12-30 | 2023-07-14 | 苏州中科先进技术研究院有限公司 | Porous polycarbazole nano film loaded with nano zero-valent iron, and preparation method and application thereof |
| CN113178338B (en) * | 2021-04-20 | 2022-11-18 | 福州大学 | Carbazolyl porous carbon/polyaniline composite electrode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304779A (en) * | 2012-03-15 | 2013-09-18 | 国家纳米科学中心 | Polycarbazole polymer as well as preparation method and applications thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6833432B2 (en) * | 2001-10-31 | 2004-12-21 | Universite Laval | Conjugated poly(2,7-carbazole) derivatives and process for the preparation thereof |
| JP4806208B2 (en) * | 2005-04-28 | 2011-11-02 | 関東化学株式会社 | Polycarbazole derivatives |
-
2016
- 2016-10-10 CN CN201610883474.4A patent/CN106378109B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103304779A (en) * | 2012-03-15 | 2013-09-18 | 国家纳米科学中心 | Polycarbazole polymer as well as preparation method and applications thereof |
Non-Patent Citations (3)
| Title |
|---|
| "A facile approach to prepare a microporous polycarbazole P-tetra(4-(N-carbazolyl)phenyl)silane network with high CO2 storage and separation properties";Fei Jiang et al.;《New Journal of Chemistry》;20160314;第40卷;第4969-4973页 |
| "Rational design and synthesis of a porous,task-specific polycarbazole for efficient CO2 capture";Tian Jin et al.;《Chemical Communication》;20160203;第52卷;第4454-4457页 |
| "有机多孔聚咔唑的制备及性能研究进展";操强等;《化学学报》;20150615(第6期);第541-556页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106378109A (en) | 2017-02-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106378109B (en) | A kind of porous polycarbazole polymer and its preparation method and application | |
| CN107428917A (en) | The modified porous super cross-linked polymer for capturing and converting for CO2 | |
| Ethiraj et al. | Solvent‐Driven Gate Opening in MOF‐76‐Ce: Effect on CO2 Adsorption | |
| CN103304779B (en) | A kind of polycarbazole polymkeric substance and its preparation method and application | |
| Yousefi et al. | Simultaneous extraction and preconcentration of uranium and thorium in aqueous samples by new modified mesoporous silica prior to inductively coupled plasma optical emission spectrometry determination | |
| Liu et al. | Zwitterionic imidazole‐urea derivative framework bridged mesoporous hybrid silica: a highly efficient heterogeneous nanocatalyst for carbon dioxide conversion | |
| Liu et al. | Facile preparation and application of luminescent cucurbit [10] uril-based porous supramolecular frameworks | |
| Kronast et al. | Gated Channels and Selectivity Tuning of CO2 over N2 Sorption by Post‐Synthetic Modification of a UiO‐66‐Type Metal–Organic Framework | |
| Ren et al. | 1, 4‐Phenylenediacetate‐based Ln MOFs–synthesis, structures, luminescence, and catalytic activity | |
| CN110016126A (en) | A kind of conjugation microporous polymer and the preparation method and application thereof | |
| Barea et al. | A flexible pro‐porous coordination polymer: Non‐conventional synthesis and separation properties towards CO2/CH4 mixtures | |
| Lee et al. | Strong Binding Affinity of a Zinc–Porphyrin‐Based Receptor for Halides through the Cooperative Effects of Quadruple C H Hydrogen Bonds and Axial Ligation | |
| He et al. | Encapsulation of an ionic metalloporphyrin into a zeolite imidazolate framework in situ for CO2 chemical transformation via host–guest synergistic catalysis | |
| CN104817577A (en) | Preparation method and catalysis applications of efficient and simple zeolite imidazole framework ZIF-8 crystals with different morphologies | |
| Maia et al. | CO 2 adsorption mechanisms on MOFs: a case study of open metal sites, ultra-microporosity and flexible framework | |
| Das et al. | Influence of hydrogen bond donating sites in UiO‐66 metal‐organic framework for highly regioselective methanolysis of epoxides | |
| Chauhan et al. | Asymmetric Organocatalytic Aza‐Friedel–Crafts Reaction of Naphthols with N‐Sulfonyl Imines | |
| Rani et al. | Metal–Organic Framework-based selective molecular recognition of organic amines and fixation of CO2 into cyclic carbonates | |
| CN109942814B (en) | Pyridyl-containing conjugated microporous polymer and preparation method and application thereof | |
| Lu et al. | Porous organic polymers containing zinc porphyrin and phosphonium bromide as bifunctional catalysts for conversion of carbon dioxide | |
| Boer et al. | A Multifunctional, Charge‐Neutral, Chiral Octahedral M12L12 Cage | |
| CN105924449A (en) | Preparation and application for reaction type fluorescein fluorescent probe capable of detecting mercury ions | |
| Cai et al. | Construction of hyper-crosslinked ionic polymers with high surface areas for effective CO2 capture and conversion | |
| CN102451756B (en) | Loaded zinc trifluoromethanesulfonate catalyst, its preparation method, and preparation method of butanone-glycol ketal | |
| Anselmo et al. | Zn‐Mediated Synthesis of 3‐Substituted Indoles Using a Three‐Component Reaction Approach |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190212 Termination date: 20211010 |