CN112159525A - Microporous network type polyimide resin, preparation method thereof and application in gas separation - Google Patents
Microporous network type polyimide resin, preparation method thereof and application in gas separation Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—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 diffusion
- B01D53/228—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 diffusion characterised by specific membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
Microporous network type polyimide resin, preparation method thereof and application in gas separation, and is mainly used for H2、N2、O2、CO2、CH4And (5) separating and purifying the micromolecular gas. The network type polyimide resin is prepared from triamine compound such as tri (4-aminophenyl) amine and the like and commercially available dianhydride (such asFIG. 1) is a diagram illustrating a low-temperature synthesis method for preparing a polyamic acid resin. Then, a polyamic acid resin film with a network structure is prepared by adopting methods such as pulling or casting molding, and the like, the polyamic acid resin film is further imidized to prepare a polyimide film, and the polyimide film is prepared by a heat treatment process. The obtained film has good gas selectivity and gas permeability. The prepared polyimide resin can effectively improve the polymer membrane material and CO due to the introduction of heteronuclear nitrogen atoms in the amine monomer2Intermolecular force among gases enables the polyimide resin film material to react with CO2/N2，CO2/CH4The separation performance of iso-gas pairs has approached or exceeded the 2008 Robeson upper limit.
Description
Technical Field
The invention belongs to the technical field of chemical industry, and relates to synthesis of microporous network type polyimide resin with good thermal stability and organic solvent resistance, a polymer film and a preparation method and application of a carbon film of the polymer film, which are suitable for H in industrial waste gas2Recovery of CO2Trapping, acid natural gas purification, air separation and the like.
Background
With the increasing consumption and continuous reduction of fossil fuels, natural gas, biogas, hydrogen and the like as typical renewable clean energy sources can bring great value to the development of human beings and society. However, these clean energy sources face the problem of product purification before transportation, storage or use, and the gas separation membrane technology is a novel green chemical separation technology for separating and purifying mixed gas by using a specific membrane, belongs to a physical process without phase change, has the advantages of simple process, low energy consumption and high efficiency, and is widely applied to numerous fields such as hydrogen recovery, natural gas purification, air separation and the like. The ideal membrane material is the key to the gas membrane separation technology. Generally, the polymer membrane material should have high permeability and good gas pair selectivity, and have the advantages of high mechanical strength, excellent plasticization resistance and thermal stability. Among the numerous membrane materials, polyimide is one of the most suitable gas separation membrane materials.
Compared with linear and hyperbranched polyimide materials, the network type polyimide material has good plasticization resistance, chemical/thermal stability and rich pore channel structures due to the unique high self-crosslinking structure, so that the material is widely applied to the field of mixed gas adsorption. However, the network type polyimide material has the characteristic of easy gelation in the preparation process, and the network structure formed after gelation is usually insoluble in common organic solvents, so that the application and development of the network type polyimide material in the field of gas separation membranes are severely limited. Therefore, the development of a preparation method of the network type polyimide film has important application value.
Disclosure of Invention
The invention aims to solve the problems that the existing network type polyimide resin film has strong rigidity, the polyimide resin film is brittle and the like, and provides a microporous network type polyimide resin, a preparation method of the resin film and a carbon film and application in gas separation.
In order to achieve the above object, the present invention specifically comprises:
1. a microporous network type polyimide resin with tri (4-aminophenyl) amine as a crosslinking point is designed and synthesized, so that the gas separation performance of the polymer material is improved by regulating and controlling the structure of a monomer.
2. Designing and synthesizing a microporous network type polyimide resin film rich in nitrogen atoms so as to improve the flexibility of a resin film material and utilize introduced heteronuclear N atoms and CO2Strong intermolecular force between gases to strengthen the membrane material to CO2/N2，CO2/CH4The separation performance of the gas pairs.
3. Provides a preparation method of the microporous polyimide resin carbon membrane.
4. Provide the gas separation performance of the microporous network type polyimide film.
5. Provides the gas separation performance of the microporous polyimide resin carbon membrane.
The technical scheme of the invention is as follows:
a low-temperature synthesis method is provided for preparing a novel microporous network polyimide resin film: triamine such as tri (4-aminophenyl) amine and the like and various dianhydrides (BTDA, PMDA, 6FDA and the like) are used as reaction raw materials, the low-temperature reaction is controlled to effectively delay the gel phenomenon, the polyamic acid resin is prepared, the homogeneous hyperbranched polyamic acid solution is placed at room temperature before the gel is not formed, the reaction temperature is obviously increased, the self-crosslinking process of the polyamic acid is accelerated, the gelation phenomenon occurs within minutes, then the solvent is slowly removed, and the network type polyimide film is prepared through chemical or thermal imidization. The film has simple preparation process and is convenient for industrialization.
The microporous network type polyimide resin provided by the invention has the following structural general formula:
in some preferred embodiments of the present invention, Ar is one of the following structural formulas:
the invention provides a series of microporous network type polyimide resins, which are specifically compounds shown as a formula XS22, a formula XS23 or a formula XS 24:
the synthetic route of the microporous network type polyimide resin is as follows:
the meaning of Ar in the above synthetic route is the same as that described above.
The preparation method of the microporous network type polyimide resin comprises the following steps:
the preparation method comprises the steps of taking tri (4-aminophenyl) amine and dianhydride (BTDA, PMDA and 6FDA) as reaction raw materials, feeding amino and anhydride (-CO-O-CO-) according to the equal molar ratio of active functional groups, carrying out polycondensation reaction at the low temperature of-60 to-50 ℃, dropwise adding an anhydride DMF solution containing the anhydride groups with the same molar amount as the amino groups into a triamine solution in the polycondensation reaction process, violently stirring for 1-6 hours under the condition to obtain a polyamide acid solution, and further removing the solvent to obtain the polyimide resin.
The preparation method comprises the following specific steps:
drying the reaction flask at 120 ℃ for 3h, cooling the flask, adding tris (4-aminophenyl) amine (TAPA), vacuumizing for 30min, replacing nitrogen for three times, adding N, N-Dimethylformamide (DMF) into the low-temperature reaction flask, stirring to dissolve, transferring the reaction system into a low-temperature environment of-60 to-50 ℃, dropwise adding an anhydride DMF solution containing equimolar amino groups after 15min, and violently stirring for 1-6 h under the condition to obtain the polyamide acid resin.
And (3) uniformly spreading the polyamic acid resin on a culture dish, slowly removing the solvent at the temperature of 50-80 ℃ under a vacuum condition, heating to the temperature of 250-350 ℃ at the heating rate of 0.5-2 ℃/min, keeping the temperature for 1-5 h to obtain a microporous network type polyimide resin film, and further carbonizing at high temperature to prepare the corresponding microporous carbon film.
The invention also provides a preparation method of the microporous network type polyimide resin film, which comprises the following preparation steps:
and pouring the synthesized polyamic acid resin into a dry culture dish, uniformly paving the polyamic acid resin on the bottom of the dish, slowly removing the solvent at the temperature of 50-80 ℃ under a vacuum condition, heating to the temperature of 250-350 ℃ at the heating rate of 0.5-2 ℃/min, and keeping the temperature for 1-5 hours to obtain the microporous network type polyamic acid film. Finally, the corresponding microporous network type polyimide resin film can be prepared by thermal imidization at a certain temperature.
The invention also provides a preparation method of the microporous network type polyimide resin carbon film, which comprises the following steps:
the synthesized microporous network type polyimide resin film is heated to a proper temperature (400-800 ℃) at a heating rate of 0.5-2 ℃/min, and is kept at the temperature for a certain time (0.5-4 h), so that the polyimide resin carbon film can be prepared.
The novel three-dimensional microporous network type polyimide resin film and the carbon film provided by the invention can be used for gas separation, and the gas separation film can be used in industrial waste gasH2Recovery of CO2Trapping, acid natural gas purification, air separation and the like.
Using 6cm2Respectively to H2、O2、CO2、N2And CH4The permeability of (a) was tested, and the test results were: h2Permeability coefficient of 26.3 to 54.5Barrer, O2The permeability coefficient of (A) is 5.0-6.4 Barrer, CO2The permeability coefficient of the alloy is 20.3-37.4 Barrer; h2/N2Selectivity of (1) is 30.2 to 48.8, O2/N2Selectivity of (5.6) to (5.7), CO2/N2Selectivity of 23.3 to 36.1, CO2/CH4The selectivity of 36.3 to 57.9.
Using 2.5cm2Respectively for N with the polyimide resin carbon film2、O2And CO2The permeability of (a) was tested, and the test results were: CO 22Has a permeability coefficient of 125.1 to 1352.6Barrer, O2The permeability coefficient of 52.4-438.8 Barrer; o is2/N2Selectivity of 1.9 to 3.7, CO2/N2The selectivity of (A) is 4.6-12.0.
The invention has the advantages and beneficial effects that:
1. the prepared polyimide resin can effectively improve the polymer membrane material and CO due to the introduction of heteronuclear nitrogen atoms in the amine monomer2Intermolecular forces between gases.
2. The prepared microporous network type polyimide resin film rich in nitrogen atoms can effectively improve the flexibility of resin film materials.
3. H in polyimide resin film2Permeability coefficient of 54.5Barrer, CO2Permeability coefficient of 37.4Barrer, O2A transmission coefficient of 6.4 Barrer; o is2/N2Selectivity coefficient of 5.6, CO2/N2Selectivity coefficient of 32.8, H2/N2Selectivity coefficient of 47.8, CO2/CH4Selectivity coefficient of 56.7.
4. H in polyimide resin carbon film2Permeability coefficient of 54.5Barrer, CO2Permeability coefficient of 37.4Barrer, O2Is disclosedThe over-coefficient is 6.4 Barrer; o is2/N2Selectivity coefficient of 5.6, CO2/N2Selectivity coefficient of 32.8, H2/N2Selectivity coefficient of 47.8, CO2/CH4Selectivity coefficient of 56.7.
Drawings
FIG. 1 shows a monomer chemical structure of a polyimide resin.
FIG. 2 is a graph showing the gas separation characteristics of a polyimide resin film of the present invention, wherein (a) a polyimide resin film O having an upper limit of Apocynum2Permeability and O2/N2Selectivity relationship, (b) polyimide resin film CO having an upper limit of Apocynum2Permeability and CO2/N2Selectivity relation, (c) polyimide resin film H having an upper limit of Apocynum2Permeability and H2/N2Selectivity relationship, (d) polyimide resin film CO having an upper limit of Apocynum2Permeability and CO2/CH4The relationship of selectivity.
FIG. 3 is a graph showing the gas separation characteristics of a polyimide resin carbon film according to the present invention, wherein (a) a polyimide resin carbon film O having an upper limit of Apocynum2Permeability and O2/N2Selectivity relation, (b) polyimide resin carbon film CO with Apocynon upper limit2Permeability and CO2/N2The relationship of selectivity.
Detailed Description
The invention will be further elucidated by means of specific embodiments in the following description, which are given by way of example and do not limit the scope of protection of the invention.
The preparation method of the gas separation membrane mainly comprises the following steps: the preparation method comprises the following steps of preparing polyimide resin, preparing a microporous network type polyimide resin film and preparing a polyimide resin carbon film.
Example 1: polyimide resin XS22
Drying the reaction flask at 120 ℃ for 3h, cooling the flask, adding 0.25g (0.861mmol) of tris (4-aminophenyl) amine (TAPA) into the flask, vacuumizing for 30min, replacing nitrogen for three times, adding N, N-Dimethylformamide (DMF) into the low-temperature reaction flask, stirring to dissolve, transferring the reaction system into a low-temperature environment at-55 ℃, dropwise adding a DMF solution containing 0.42g (1.292mmol) of BTDAP after 15min, and vigorously stirring for 3h under the condition to prepare the polyamic acid solution. Further removing the solvent, and heating at 300 ℃ for 2h to obtain polyimide resin XS 22.
Example 2: polyimide resin XS23
Drying the reaction flask at 120 ℃ for 3h, cooling the flask, adding 0.2g (0.689mmol) of tris (4-aminophenyl) amine (TAPA), vacuumizing for 30min, replacing nitrogen for three times, adding N, N-Dimethylformamide (DMF) into the low-temperature reaction flask, stirring to dissolve, transferring the reaction system into a low-temperature environment at-55 ℃, dropwise adding a DMF solution containing 0.23g (1.033mmol) of PMDA after 15min, and vigorously stirring for 3h under the condition to prepare the polyamic acid solution. Further removing the solvent, and heating at 300 ℃ for 2h to obtain polyimide resin XS 23.
Example 3: polyimide resin XS24
Drying the reaction flask at 120 ℃ for 3h, cooling the flask, adding 0.20g (0.689mmol) of tris (4-aminophenyl) amine (TAPA), vacuumizing for 30min, replacing nitrogen for three times, adding N, N-Dimethylformamide (DMF) into the low-temperature reaction flask, stirring to dissolve, transferring the reaction system into a low-temperature environment at-55 ℃, dropwise adding a DMF solution containing 6FDA0.46g (1.033mmol) after 15min, and vigorously stirring for 3h under the conditions to prepare the polyamic acid solution. Further removing the solvent, and heating at 300 ℃ for 2h to obtain polyimide resin XS 24.
Example 4: polyimide resin film FilmXS22
Pouring the polyamic acid solution prepared in the embodiment 1 into a dry culture dish, uniformly paving the bottom of the dish, removing the solvent at 60 ℃ in vacuum until a film is formed, peeling the obtained film, and then performing thermal imidization at 300 ℃ for 2h (at a heating rate of 0.5-2 ℃/min) to obtain the microporous network type polyimide resin film FilmXS 22.
Example 5: polyimide resin film FilmXS23
Pouring the polyamic acid solution prepared in the embodiment 2 into a dry culture dish, uniformly paving the bottom of the dish, removing the solvent at 60 ℃ in vacuum until a film is formed, peeling the obtained film, and then performing thermal imidization at 300 ℃ for 2h (at a heating rate of 0.5-2 ℃/min) to obtain the microporous network type polyimide resin film FilmXS 23.
Example 6: polyimide resin film FilmXS24
Pouring the polyamic acid solution prepared in the embodiment 3 into a dry culture dish, uniformly paving the bottom of the dish, removing the solvent at 60 ℃ in vacuum until a film is formed, peeling the obtained film, and then performing thermal imidization at 300 ℃ for 2h (at a heating rate of 0.5-2 ℃/min) to obtain the microporous network type polyimide resin film FilmXS 24.
Example 7: polyimide resin carbon film CarbonfilmXS22
The microporous network type polyimide resin film FilmXS22 obtained in example 4 is heated to 550 ℃ at the heating rate of 2 ℃/min and is kept at the temperature for 2h, and then the microporous polyimide resin carbon film CarbonfilmXS22 can be prepared.
Example 8: polyimide resin carbon film CarbonfilmXS23
The microporous network type polyimide resin film FilmXS23 obtained in the example 5 is heated to 550 ℃ at the heating rate of 2 ℃/min and is kept for a certain time of 2h at the temperature, and then the microporous polyimide resin Carbon film Carbon filmXS23 can be prepared.
Example 9: polyimide resin carbon film CarbonfilmXS24
Microporous polyimide resin carbon film CarbonfilmXS24 can be prepared by heating the microporous network type polyimide resin film FilmXS24 obtained in example 6 to 550 ℃ at a heating rate of 2 ℃/min and maintaining the temperature for 2 h.
Example 10: gas separation characteristic test of polyimide resin film
The gas separation characteristic test method of the polyimide resin film is a constant volume variable pressure method: under the conditions of 302.15K and 0.2MPa working pressure, 6cm is used2Respectively testing CH with polyimide film4、N2、O2、CO2And H2Permeability of (2). The test results of the film are as follows: h2Permeability coefficient of 26.3 to 54.5Barrer, O2Has a permeability coefficient of about 5.0 to 6.4Barrer, CO2The permeability coefficient of the alloy is 20.3-37.4 Barrer; h2/N2Selectivity of (1) is 30.2 to 48.8, O2/N2Selectivity of (5.6) to (5.7), CO2/N2Selectivity of 23.3 to 36.1, CO2/CH4The selectivity of 36.3 to 57.9. Among them, the polyimide resin film FilmXS24 has the best gas separation performance, and H2Permeability coefficient of 54.5Barrer, CO2Permeability coefficient of 37.4Barrer, O2A transmission coefficient of 6.4 Barrer; o is2/N2Selectivity coefficient of 5.6, CO2/N2Selectivity coefficient of 32.8, H2/N2Selectivity coefficient of 47.8, CO2/CH4Selectivity coefficient of 56.7.
Example 11: gas separation performance test of polyimide resin carbon membrane
The gas separation characteristic test method of the polyimide resin carbon membrane is a constant volume variable pressure method: under the working pressure conditions of 302.15K and 0.2MPa, 2.5cm is used2Respectively testing the polyimide films of2、O2And CO2Permeability of (2). The test results were as follows: CO 22Has a permeability coefficient of 125.1 to 1352.6Barrer, O2The permeability coefficient of 52.4-438.8 Barrer; o is2/N2Selectivity of 1.9 to 3.7, CO2/N2The selectivity of (A) is 4.6-12.0. Wherein, the polyimide resin carbon film XS24 has the best gas separation performance, and CO21352.6Barrer, O2438.8 Barrer; o is2/N2Selectivity of about 3.6, CO2/N2Selectivity of (a) is about 11.1. The results of gas separation performance are shown in FIGS. 2 and 3, gas vs. CO2/N2，CO2/CH4The separation performance of (a) is close to the upper limit of Robeson in 2008. Test results show that the prepared polyimide resin film and the carbon film thereof have good gas permeability coefficient and gas selectivity and show great industrial application potential.
Claims (8)
1. A microporous network type polyimide resin characterized by having the following chemical structure:
wherein Ar is one of the following structural formulas:
2. the microporous network polyimide resin of claim 1, wherein the polyimide resin is a compound of formula XS22, formula XS23, or formula XS 24:
3. the method for preparing microporous network type polyimide resin according to claim 1, wherein the starting material is tris (4-aminophenyl) amine and dianhydride are reacted with each other through the amino group (-NH) which is a reactive functional group of triamine2) Feeding with dianhydride group (-CO-O-CO-) of dianhydride in equimolar ratio, and performing polycondensation reaction at low temperature to obtain the final product, wherein the dianhydride is BTDA, PMDA or 6FDA, but not limited to the threeA dianhydride.
4. The method for preparing microporous network type polyimide resin according to claim 3, wherein the temperature of the polycondensation reaction is-60 to-50 ℃, the polycondensation reaction process is that an anhydride DMF solution containing an anhydride group with an equimolar amount to an amino group is dropwise added into a triamine solution, the mixture is vigorously stirred for 1 to 6 hours under the condition, a polyamic acid solution is obtained, and the polyimide resin is obtained after further removing the solvent.
5. A preparation method of a microporous network type polyimide resin film is characterized by comprising the following steps: uniformly spreading the polyamic acid solution synthesized in the claim 4 on a culture dish, slowly removing the solvent under the vacuum condition of 50-80 ℃, then heating to 250-350 ℃ at the heating rate of 0.5-2 ℃/min, and keeping the temperature for 1-5 h to obtain the microporous network type polyimide resin film.
6. Use of the microporous network type polyimide resin film obtained by the method according to claim 5 for gas separation, wherein: at a pressure of 0.2MPa, H2Permeability coefficient of 26.3 to 54.5Barrer, O2Permeability coefficient of 5.0-6.4 Barrer, CO2The permeability coefficient of the alloy is 20.3-37.4 Barrer; h2/N2Selectivity of (1) is 30.2 to 48.8, O2/N2Selectivity of (5.6) to (5.7), CO2/N2Selectivity of 23.3 to 36.1, CO2/CH4The selectivity of 36.3 to 57.9.
7. A preparation method of a microporous network type polyimide resin carbon film is characterized by comprising the following steps: the microporous network type polyimide resin film synthesized according to claim 5 is heated to a temperature of 400 to 800 ℃ at a heating rate of 0.5 to 2 ℃/min and is kept at the temperature for 0.5 to 4 hours to prepare a microporous polyimide resin carbon film.
8. The method of separating gas by using the microporous network type polyimide resin carbon membrane prepared by the method of claim 7Use, characterized in that: at a pressure of 0.2MPa, CO2Has a permeability coefficient of 125.1 to 1352.6Barrer, O2The permeability coefficient of 52.4-438.8 Barrer; o is2/N2Selectivity of 1.9 to 3.7, CO2/N2The selectivity of (A) is 4.6-12.0.
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