CN114797506A - Preparation method and application of ionized polyimide gas separation membrane - Google Patents
Preparation method and application of ionized polyimide gas separation membrane Download PDFInfo
- Publication number
- CN114797506A CN114797506A CN202110080805.1A CN202110080805A CN114797506A CN 114797506 A CN114797506 A CN 114797506A CN 202110080805 A CN202110080805 A CN 202110080805A CN 114797506 A CN114797506 A CN 114797506A
- Authority
- CN
- China
- Prior art keywords
- polyimide
- ionized
- gas separation
- solution
- separation membrane
- 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.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- 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
-
- 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
- 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
- C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a preparation method and application of an ionized polyimide gas separation membrane, and belongs to the fields of polymer materials and gas separation membranes. The polymer is prepared by synthesizing polyimide by using diamine containing imidazole rings and monomers with different dianhydride structures through solution copolymerization condensation, and obtaining an ionized polyimide film material through imidazole ring functionalized modification and ion exchange. The prepared ionized polyimide is spun by coating or dry spraying-wet spinningThe silk method yields flat or hollow fiber gas separation membranes. The invention effectively inhibits the plasticizing effect of the polyimide gas separation membrane material by forming the ionic electrostatic physical crosslinking effect between molecular chains, and increases CO 2 And H 2 The separation selectivity of acid gases such as S and the like and the processability of the polyimide film material. The separation membrane prepared by the invention has good gas separation performance and stability, and can be applied to natural gas decarburization and CO in flue gas 2 Trapping, air separation, hydrogen separation and recovery.
Description
Technical Field
The invention relates to a preparation method and application of an ionized polyimide gas separation membrane, belonging to the technical field of polyimide materials and gas separation membranes.
Background
The gas separation membrane technology has the advantages of high energy efficiency, environmental protection, small occupied area, simple and convenient equipment, easy regulation and control and the like, and is more and more widely concerned. The core of the gas separation membrane technology is a membrane material, and polyimide is regarded as an excellent gas separation membrane material due to a series of advantages of good heat resistance, stability, higher mechanical strength, good chemical corrosion resistance and the like. Ideal polyimide gas separation membrane materials are generally required to have high gas separation selectivity and permeability, and in addition, good processability and stability. Although the polyimide has a wide application prospect in the field of gas separation, few types of polyimide can be commercialized at present, wherein gas separation performance and polymer dissolution processability are important reasons limiting large-scale application of the polyimide, and therefore, the development of a polyimide film material with better separation performance and processability is a focus of research in the field of gas separation membranes at present.
Ionic liquids are low temperature molten salts composed of organic cations and organic or inorganic anions. Since the ionic liquid has rich charge effect and dipole effect, the ionic liquid has CO 2 ,H 2 And the acid gases such as S and the like have very good solubility and dissolution selectivity. Thus, the charge effect of ionic liquids is combined with the excellent gas separation and mechanical properties of polyimides to enhance CO through charge effect and dipolar action 2 The solubility and the dissolution selectivity of acid gases in the membrane are equal, and the solubility and the processability of the polyimide membrane material are improved through the dipole effect, or the application range and the field of the polyimide gas separation membrane are greatly expanded.
At present, there is a research on improving the separation performance of polyimide by performing functional modification on the polyimide. Chinese patent CN1760236A prepared sulfonate functionalized polyimide film material from two tetracarboxylic dianhydrides and 3, 5-diamino-2, 4, 6-trimethylbenzene sulfonic acid, which has better solubility in the mixed solution of absolute ethanol and distilled water, but relatively low permeability and selectivity. Chinese patent CN108993180A prepares a grafted polyion liquid polyimide membrane, the imino of the polyimide polymer is used as a grafting site for functional grafting, and the prepared membrane has low gas separation selectivity. Chinese patent CN108114615A adopts a solution copolymerization method of 6FDA and MPDSAM to synthesize polyimide (6FDA-MPDSAM) containing sulfonate, and the material has higher carbon dioxide/methane selectivity but lower carbon dioxide permeability. No patent report of ionizing polyimide containing imidazolium salt is found.
Disclosure of Invention
The invention aims to provide a modified ionized polyimide gas separation membrane material which can be used for industrySeparation of important gas mixtures, in particular with excellent CO 2 Separation performance and polymer dissolution processability.
To achieve the above object, the present invention provides an ionized polyimide gas separation membrane comprising a general structural formula shown in formula 1:
wherein R is 1 Containing functional groups R a ,R b ,R c ,R d ,R e ,R f Any one or more of R 2 Containing functional groups R g ,R h ,R i ,R j Any one or more of R 3 Containing functional groups R a ,R b ,R c ,R d ,R e ,R f Any one or more of. The imidazolium salt anion X - Represents Cl — ，Br — ，I — ，NTf 2 — ，H 2 PO 4 — ，BF 4 — , PF6 — One or more of (a).
The invention also provides a preparation method of the ionized polyimide film material, which comprises the following steps: (1) preparing a polyimide copolymer; (2) preparing an ionized polyimide film material; (3) ion exchange reaction; (4) and (3) preparing an ionized polyimide gas separation membrane. The specific reaction route is as follows:
the specific synthesis method of the polyimide copolymer in the step (1) comprises the following steps: dissolving diamine monomer in solvent A until the diamine monomer is completely dissolved, then adding dianhydride monomer, and stirring for 6-12h at 0-50 ℃ in nitrogen atmosphere to obtain the polyamic acid solution. Imidizing the obtained polyamic acid solution by using a dehydrating agent B and a catalyst C, reacting for 12-24h, cooling, adding an excessive precipitator D, washing, and drying in vacuum at the temperature of 100-150 ℃ to obtain the polyimide copolymer.
In the step (2), the polyimide is subjected to ionization reaction, and the specific synthesis steps are as follows: the polyimide polymer was dissolved in the anhydrous solvent a at room temperature under an inert atmosphere and stirred, and the halide was injected into the reaction solution and sealed. The temperature was raised to 50 ℃ and stirred for more than 12 hours.
In the step (3), the ion exchange reaction comprises the following specific synthetic steps: dissolving the polymer obtained in the step (2) in 5 wt% of the solution A, dissolving inorganic salt with twice molar equivalent in 10-30 wt% of the solution A, dropwise adding the inorganic salt solution into the ionized polyimide solution, and stirring and reacting for 24 hours at normal temperature. The solution is precipitated in a solvent D, washed and dried at a temperature of 80-100 ℃ to obtain the ionized polyimide with different anions.
The preparation method of the ionized polyimide gas separation membrane in the step (4) comprises the following preparation processes: dissolving ionized polyimide in an organic solvent, casting the ionized polyimide on a polymer base membrane to enable the ionized polyimide to flow along, volatilizing the solvent and drying to obtain an ionized polyimide gas separation flat membrane; or the prepared polyimide solution is subjected to dry spraying-wet spinning to obtain a hollow fiber membrane, and then the hollow fiber membrane is subjected to solvent removal and drying to obtain the polyimide copolymer hollow fiber gas separation membrane.
In the preparation process of the ionized polyimide gas separation membrane, the solvent A is one or more of N, N-dimethylacetamide (DMAc), N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO); the dehydrating agent B is one or more of acetic anhydride, 1, 2-dichlorobenzene, toluene and xylene; the catalyst C is one or more of pyridine and isoquinoline; the precipitator D is one or more of methanol, ethanol or acetone; the halide is one or more of methyl iodide and ethyl iodide; the inorganic salt is NH 4 Cl,LiTFSI,NaH 2 PO 4 ,NaBF 4 ,LiPF 6 One or more of (a).
The ionized polyimide gas separation membrane is mainly used for decarbonization of natural gas and CO in flue gas 2 Trapping, air separation, hydrogen recovery, and the like.
Detailed Description
The present invention will be described in more detail with reference to examples, but the embodiments of the present invention are not limited thereto.
Example 1
1. Under the protection of nitrogen, 2,4, 6-trimethyl-1, 3-phenylenediamine (1.3375g,8.9mmol) and 2- (4-aminophenyl) -5-aminobenzimidazole (2.0000g,8.9mmol) were added to a 250mL three-necked flask equipped with a mechanical stirrer, and then anhydrous NMP (50mL) was added thereto, and after the diamine was completely dissolved, pyromellitic dianhydride (3.8841g,17.8mmol) was added and reacted at 20 ℃ for 4 hours to obtain the corresponding polyamic acid solution.
2. Adding 0.7g of isoquinoline and 25mL of 1, 2-dichlorobenzene into the polyamic acid solution obtained in the step 1, and continuously reacting at the temperature of 175-; and after cooling, slowly pouring the obtained polyimide solution into the stirred anhydrous methanol, washing and filtering the precipitate for multiple times by using the anhydrous methanol, and continuously drying for 12 hours at the temperature of 120 ℃ in vacuum to obtain the polyimide solid.
3. Anhydrous DMF (50mL) was added to a 100mL single-neck flask, polyimide (2g,3.2mmol) was dissolved in the solvent, methyl iodide (0.9084g,6.4mmol) was added and the vial was sealed and reacted for 30h at 80 ℃ protected from light;
4. reacting NaH with 2 PO 4 (1.5355g,12.8mmol) was added to the ionized polyimide-containing DMSO and stirring was continued at room temperature for 12 h. After cooling the resulting solution to room temperature, it was precipitated in excess ether, washed several times repeatedly, and dried under vacuum at 50 ℃ for 12h to give an ionized polyimide solid.
4. The polyimide solid obtained in step 2 was dissolved in DMF and THF at room temperature to prepare a 32% polyimide solution.
5. And (3) carrying out dry-jet-wet spinning on the polyimide solution prepared in the step (3) to obtain a hollow fiber membrane, and soaking the hollow fiber membrane in methanol and normal hexane to obtain the polyimide hollow fiber gas separation membrane.
Example 2
1. In a 100mL three-necked flask equipped with a mechanical stirrer, under the protection of nitrogen, 2- (4-aminophenyl) -5-aminobenzimidazole (2.0000g,8.9mmol) and 1, 3-diamino-2-methylbenzene (1.0870g, 8.9mmol) were added, then anhydrous NMP (50mL) was added, after the diamine was completely dissolved, hexafluorodianhydride (7.8769 g,17.8mmol) was added, and after 5 hours of reaction at room temperature, the corresponding polyamic acid solution was obtained.
2. Adding 0.7g of isoquinoline and 24mL of toluene into the polyamic acid solution obtained in the step 1, and continuously reacting at the temperature of 175-200 ℃ for 12-24h to obtain a polyimide solution; then the obtained polyimide solution is slowly poured into anhydrous methanol which is stirred, and the precipitate is washed and filtered for a plurality of times by the anhydrous methanol and is continuously dried for 12 hours at the vacuum temperature of 150 ℃ to obtain the polyimide solid.
3. Anhydrous DMSO (50mL) was added to a 100mL single-neck flask, polyimide (2.0000g,3.0 mmol) was dissolved in the solvent, iodomethane (0.8516g,6.0mmol) was added and the vial was sealed and reacted for 30 hours at 80 ℃ protected from light.
4. At room temperature, reacting NH 4 Cl (0.6847g,12.8mmol) was added to the ionized polyimide containing DMSO and stirring was continued at room temperature for 12 h. After cooling the resulting solution to room temperature, it was precipitated in excess ether, washed several times repeatedly, and dried under vacuum at 50 ℃ for 12h to give an ionized polyimide solid.
5. And (3) dissolving the ionized polyimide solid obtained in the step (3) in DMF at room temperature to prepare an ionized polyimide solution with the concentration of 2%, pouring the solution into a glass vessel with a certain size, uniformly casting, volatilizing the solvent at room temperature, and removing the membrane to obtain the ionized polyimide gas separation membrane.
6. The thickness of the film thus obtained is 40 to 60 μm, and He and H were measured at 0.2MPa and 35 ℃ 2 、 N 2 、O 2 、CH 4 And CO 2 Permeability of six pure gases, respectively31.24barrer, 27.80barrer, 0.46 barrer, 2.59barrer, 0.25barrer, 13.64barrer, then H 2 /N 2 Selectivity is 60.30, H 2 /CH 4 Selectivity is 110.75 He/N 2 The selectivity is 67.77, He/CH 4 Selectivity is 124.46, O 2 /N 2 Selectivity of 5.63, CO 2 /N 2 Selectivity 29.59, CO 2 /CH 4 The selectivity was 54.34. CO 2 2 :CH 4 1:1(V: V) mixed gas anti-plasticizing effect pressure>3.0MPa。
Example 3
1. Under the protection of nitrogen, 2- (4-aminophenyl) -5-aminobenzimidazole (1.5000g,6.7mmol) and 1, 3-diamino-2, 4, 6-trimethylbenzene (1.0025g,6.7mmol) are added into a 250mL three-neck flask provided with a mechanical stirrer, then anhydrous NMP (50mL) is added, after the diamine is completely dissolved, hexafluorodianhydride (5.9077g,13.4mmol) is added, and after 5 hours of reaction at room temperature, the corresponding polyamic acid solution is obtained.
2. Adding 0.5g of isoquinoline and 16mL of toluene into the polyamic acid solution obtained in the step 1, and continuously reacting at the temperature of 175-200 ℃ for 12-24h to obtain a polyimide solution; then, the obtained polyimide solution is slowly poured into anhydrous methanol which is stirred, and precipitates are washed and filtered for multiple times by the anhydrous methanol and are continuously dried for 12 hours at the vacuum temperature of 150 ℃ to obtain polyimide solid.
3. Anhydrous DMSO (50mL) was added to a 100mL single-neck flask, polyimide (2.0000g,3.2 mmol) was dissolved in the solvent, iodomethane (0.9084g,6.4mmol) was added and the vial was sealed and reacted for 30h at 80 ℃ protected from light.
4. LiTFSI (3.7896g,13.2mmol) was added to the ionized polyimide containing DMSO at room temperature and stirring was continued for 12h at room temperature. After cooling the resulting solution to room temperature, it was precipitated in excess ether, washed several times repeatedly, and dried under vacuum at 50 ℃ for 12h to give an ionized polyimide solid. 5. And (3) at room temperature, dissolving the ionized polyimide solid obtained in the step (4) in DMF to prepare a polyimide solution with the concentration of 2%, pouring the solution into a glass vessel with a certain size, uniformly extending, volatilizing the solvent at room temperature, and removing the membrane to obtain the polyimide gas separation membrane.
6. The thickness of the film thus obtained is 40 to 60 μm, and He and H were measured at 0.2MPa and 35 ℃ 2 、 N 2 、O 2 、CH 4 And CO 2 Permeability of six pure gases, 41.86barrer, 45.82barrer, 0.89 barrer, 4.55barrer, 0.52barrer, 24.27barrer, respectively, then H 2 /N 2 Selectivity was 51.31, H 2 /CH 4 Selectivity of 87.45, He/N 2 The selectivity is 46.87, He/CH 4 Selectivity is 79.88, O 2 /N 2 Selectivity 5.09, CO 2 /N 2 Selectivity 29.59, CO 2 /CH 4 The selectivity was 54.34. CO 2 2 :CH 4 1:1(V: V) mixed gas anti-plasticizing effect pressure>2.8MPa。
Claims (8)
1. An ionized polyimide gas separation membrane having the general structural formula:
the method is characterized in that: r 1 Containing functional groups R a ,R b ,R c ,R d ,R e ,R f Any one or more of, R 2 Containing functional groups R g ,R h ,R i ,R j Any one or more of R 3 Containing functional groups R a ,R b ,R c ,R d ,R e ,R f Any one or more of; x - Represents Cl — ，Br — ，I — ，NTf 2 — ，H 2 PO 4 — ，BF 4 — ,PF6 — One or more of (a).
2. The ionized polyimide gas separation membrane of claim 1, wherein: the dianhydride monomer is selected from pyromellitic dianhydride (PMDA), 4, 4-diphenyl ether dianhydride (ODPA), 3,3',4,4' -biphenyltetracarboxylic dianhydride (BPDA), 4,4- (hexafluoroisopropylene) diphthalic anhydride (6FDA), 3,3',4,4' -benzophenonetetracarboxylic dianhydride (BTDA), and 1,4,5, 8-naphthalenetetracarboxylic anhydride (NTDA). The diamine monomer is selected from 1, 3-diamino-2, 4, 6-trimethylbenzene, 1, 4-diamino-2, 3,5, 6-tetramethylbenzene, 2, 2-bis (3-amino) hexafluoropropane and 1, 3-diamino-2-methylbenzene.
3. The ionized polyimide gas separation membrane of claim 1, wherein: the proportion of imidazolium salt units in the diamine monomer, i.e. n/(m + n), is 0-100%, preferably > 50%; wherein 1< m <1000, 1< n < 1000.
4. The method for preparing an ionized polyimide gas separation membrane material according to claim 1, characterized by the steps of:
(1) preparation of polyimide copolymer:
and dissolving a diamine monomer in the solvent A until the diamine monomer is completely dissolved, adding a dianhydride monomer, and stirring for 6-12 hours at 0-50 ℃ in a nitrogen atmosphere to obtain a polyamic acid solution. Imidizing the obtained polyamic acid solution by using a dehydrating agent B and a catalyst C, reacting for 12-24h, cooling, adding an excessive precipitator D, washing, and drying in vacuum at the temperature of 100-150 ℃ to obtain the polymer.
(2) Polyimide ionization reaction
The polyimide polymer was dissolved in the anhydrous solvent a at room temperature under an inert atmosphere and stirred, and the halide was injected into the reaction solution and sealed. The temperature is increased to 50 ℃, stirred for more than 12h, cooled to room temperature, added into excessive precipitator D, washed and dried in vacuum at the temperature of 100 ℃ and 150 ℃ to obtain the ionized polyimide.
(3) Ion exchange reaction
Dissolving the polymer obtained in the step (2) in 5 wt% of the solution A, dissolving inorganic salt with twice molar equivalent in 30 wt% of the solution A, dropwise adding the inorganic salt solution into the ionized polyimide solution, and stirring and reacting for 24 hours at normal temperature. The solution is precipitated in a solvent D, washed and dried at a temperature of 80-100 ℃ to obtain the ionized polyimide with different anions.
5. The method for preparing an ionized polyimide film material according to claim 4, wherein: the anhydrous solvent A is one or more of N, N-dimethylacetamide (DMAc), N, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO). The dehydrating agent B is one or more of acetic anhydride, 1, 2-dichlorobenzene, toluene and xylene, the catalyst C is one or more of pyridine and isoquinoline, and the precipitator D is methanol, ethanol or acetone. The halide is methyl iodide or ethyl iodide. The inorganic salt is NH 4 Cl,LiTFSI,NaH 2 PO 4 ,NaBF 4 ,LiPF 6 One or more of (a).
6. The ionized polyimide gas separation membrane of claim 1, wherein: the gas separation membrane is in the form of a flat membrane or a hollow fiber membrane.
7. The method for producing a flat sheet membrane according to claim 6, wherein: and filtering the prepared ionized polyimide solution, coating the ionized polyimide solution on an inorganic or polymer base membrane for tape casting, volatilizing the solvent and drying to obtain the ionized polyimide gas separation flat membrane. The hollow fiber membrane is prepared by dry-spraying and wet-spinning the prepared ionic liquid polyimide solution to obtain the hollow fiber membrane, and then removing the solvent and drying to obtain the ionized polyimide hollow fiber gas separation membrane.
8. The ionized polyimide gas separation membrane of claim 1, used primarily for natural gas decarbonization, CO in flue gas 2 Trapping, air separation, hydrogen recovery, and the like.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110080805.1A CN114797506B (en) | 2021-01-21 | 2021-01-21 | Preparation method and application of ionized polyimide gas separation membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110080805.1A CN114797506B (en) | 2021-01-21 | 2021-01-21 | Preparation method and application of ionized polyimide gas separation membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114797506A true CN114797506A (en) | 2022-07-29 |
| CN114797506B CN114797506B (en) | 2023-08-01 |
Family
ID=82523998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110080805.1A Active CN114797506B (en) | 2021-01-21 | 2021-01-21 | Preparation method and application of ionized polyimide gas separation membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114797506B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116144176A (en) * | 2023-04-19 | 2023-05-23 | 山东华夏神舟新材料有限公司 | Polyimide composition, film, preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110192281A1 (en) * | 2008-10-07 | 2011-08-11 | National University Of Singapore | Polymer blends and carbonized polymer blends |
| CN105348201A (en) * | 2015-11-17 | 2016-02-24 | 中国科学院长春应用化学研究所 | Hydroxyl-containing benzimidazole diamines and preparation method thereof |
| US20160199790A1 (en) * | 2013-09-20 | 2016-07-14 | Fujifilm Corporation | Gas separation membrane, gas separation module, gas separation device, and gas separation method |
| US20160263534A1 (en) * | 2015-03-11 | 2016-09-15 | The Board Of Regents Of The University Of Texas System | Compatibilized immiscible polymer blends and molecular sieve membranes thereof |
| CN108993180A (en) * | 2018-08-22 | 2018-12-14 | 大连理工大学 | A kind of graft type poly ion liquid polyimide film and preparation method thereof |
| CN110606951A (en) * | 2019-10-15 | 2019-12-24 | 中国科学院过程工程研究所 | Semi-aromatic polyimide, preparation method and application thereof, and gas separation membrane comprising semi-aromatic polyimide |
-
2021
- 2021-01-21 CN CN202110080805.1A patent/CN114797506B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110192281A1 (en) * | 2008-10-07 | 2011-08-11 | National University Of Singapore | Polymer blends and carbonized polymer blends |
| US20160199790A1 (en) * | 2013-09-20 | 2016-07-14 | Fujifilm Corporation | Gas separation membrane, gas separation module, gas separation device, and gas separation method |
| US20160263534A1 (en) * | 2015-03-11 | 2016-09-15 | The Board Of Regents Of The University Of Texas System | Compatibilized immiscible polymer blends and molecular sieve membranes thereof |
| CN105348201A (en) * | 2015-11-17 | 2016-02-24 | 中国科学院长春应用化学研究所 | Hydroxyl-containing benzimidazole diamines and preparation method thereof |
| CN108993180A (en) * | 2018-08-22 | 2018-12-14 | 大连理工大学 | A kind of graft type poly ion liquid polyimide film and preparation method thereof |
| CN110606951A (en) * | 2019-10-15 | 2019-12-24 | 中国科学院过程工程研究所 | Semi-aromatic polyimide, preparation method and application thereof, and gas separation membrane comprising semi-aromatic polyimide |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116144176A (en) * | 2023-04-19 | 2023-05-23 | 山东华夏神舟新材料有限公司 | Polyimide composition, film, preparation method and application thereof |
| CN116144176B (en) * | 2023-04-19 | 2023-08-15 | 山东华夏神舟新材料有限公司 | Polyimide composition, film, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114797506B (en) | 2023-08-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105289337B (en) | A kind of crosslinkable polyimide gas separation membrane and preparation method | |
| US5725633A (en) | Sulfonated polyimide gas separation membranes | |
| KR100205963B1 (en) | Novel soluble polyimide resin for liquid crystal orientation film | |
| CN108114615A (en) | A kind of polyimide gas separating film material and preparation and application | |
| CN106279685A (en) | Polyimide material, its preparation method and application of based on Teller lattice alkali structure | |
| CN108043232A (en) | A kind of hexatomic ring polyimide copolymer seperation film and its preparation method and application | |
| CN107098913A (en) | 5,10,15,20 4 [4 [（3 aminophenyls）Acetenyl] phenyl] porphyrin and synthetic method and application | |
| CN107573501A (en) | A kind of cross-linking fluorine-containing sulfonated polyether compound and preparation method thereof | |
| CN114797506B (en) | Preparation method and application of ionized polyimide gas separation membrane | |
| CN109833784A (en) | A kind of Silicone Containing Polyimides gas separation membrane and preparation method | |
| CN114395127A (en) | Polyimide resin for fluorine-containing gas separation and preparation method thereof | |
| CN104371102B (en) | Negative photo-sensitive polyimide and method for preparing same | |
| CN110591092B (en) | Polyimide high polymer material based on 2, 5-diallyloxy p-phenylenediamine monomer and preparation method thereof | |
| CN110713598A (en) | Preparation method of soluble low-temperature imidized polyimide | |
| CN115715939A (en) | Polyimide mixed matrix membrane and preparation method and application thereof | |
| CN114591503B (en) | Soluble poly (benzimidazole-co-imide) polymer and preparation and application thereof | |
| CN113831582B (en) | Cross-linked polyimide-based composite aerogel and preparation method thereof | |
| KR20200066446A (en) | BCDA-based semi-alicyclic polyimide membrane materials for gas separation and the preparation method thereof | |
| CN114797507B (en) | Structure, preparation method and application of polyimide copolymer gas separation membrane with plasticizing effect resistance | |
| CN116272441B (en) | Structure and preparation method of gas separation membrane for natural gas helium stripping and plasticizing resistance effect | |
| CN107903417A (en) | The preparation and its application of the side chain type sulfonated polyimides of quinoxaline group bridge joint | |
| JP3698107B2 (en) | Novel separation membrane and method for producing the same | |
| Wang et al. | Synthesis and characterization of sulphonated polymer derived from 6FDA-ODA polyimide | |
| CN113244788A (en) | Synthetic method and application of polyimide gas separation membrane material | |
| Qian et al. | Six-membered ring copolyimides as novel high performance membrane materials for gas separations |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |