CN101700474B - Polyimide gas separation membrane with high molecular weight and preparation method thereof - Google Patents
Polyimide gas separation membrane with high molecular weight and preparation method thereof Download PDFInfo
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- CN101700474B CN101700474B CN2009102387893A CN200910238789A CN101700474B CN 101700474 B CN101700474 B CN 101700474B CN 2009102387893 A CN2009102387893 A CN 2009102387893A CN 200910238789 A CN200910238789 A CN 200910238789A CN 101700474 B CN101700474 B CN 101700474B
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 58
- 239000004642 Polyimide Substances 0.000 title claims abstract description 46
- 238000000926 separation method Methods 0.000 title claims abstract description 29
- 239000012528 membrane Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 34
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 18
- 125000003118 aryl group Chemical group 0.000 claims abstract description 15
- 239000002798 polar solvent Substances 0.000 claims abstract description 10
- 150000004984 aromatic diamines Chemical class 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 239000011521 glass Substances 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 7
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 5
- -1 propionic andydride Chemical compound 0.000 claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 230000002045 lasting effect Effects 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- RDMFEHLCCOQUMH-UHFFFAOYSA-N 2,4'-Diphenyldiamine Chemical group C1=CC(N)=CC=C1C1=CC=CC=C1N RDMFEHLCCOQUMH-UHFFFAOYSA-N 0.000 claims description 2
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001896 cresols Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940090668 parachlorophenol Drugs 0.000 claims description 2
- DUCKXCGALKOSJF-UHFFFAOYSA-N pentanoyl pentanoate Chemical compound CCCCC(=O)OC(=O)CCCC DUCKXCGALKOSJF-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000005516 engineering process Methods 0.000 abstract description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003345 natural gas Substances 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract 1
- 239000003209 petroleum derivative Substances 0.000 abstract 1
- 238000009835 boiling Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- BBTGUNMUUYNPLH-UHFFFAOYSA-N 5-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 BBTGUNMUUYNPLH-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 150000003949 imides Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention discloses a polyimide gas separation membrane with high molecular weight and a preparation method thereof, the polyimide gas separation membrane consists of aromatic diamine and aromatic dianhydride, a polar solvent is used for matching, and the polyimide gas separation membrane with the high molecular weight is prepared by the technological steps of preparing polyamic acid solution, preparing a polyimide membrane and stripping the polyimide membrane, thereby preparing the polyimide gas separation membrane with the high molecular weight. The polyimide gas separation membrane has the advantages of strong solubility, high molecular weight, good permeability, stable performances, good membrane-forming property, easy processing and molding, simple preparation technology, low cost and easy industrialization, and can be extensively applied in CO2/CH4 and CO2/H2 separation in petroleum and natural gas and be suitable for popularization.
Description
Affiliated technical field
The present invention relates to technical field of polymer materials, be specifically related to a kind of polyimide gas separation membrane with high molecular weight and preparation method.
Technical background
In technical field of polymer materials; Polyimide material is a kind of high-performance polymer material with imide ring architectural characteristic; Have excellent hear resistance, anti-irradiation, excellent mechanical performance and electric property etc., be widely used in technical fields such as Aeronautics and Astronautics, automobile, petrochemical industry.Wherein polyimide gas separating film is that polyimides is used one of material comparatively widely.It is a kind of " green technology " that the polyimides gas film separates; And owing to advantages such as it have low energy consumption, environmental friendliness, process is simple, easy to operate, separation property is strong; With the competition of traditional isolation technics (absorption, absorption, cryogenic separation etc.) in demonstrate special advantages, its research is very rapid with application development.Yet polyimides has good separation selectivity usually, but most of polyimides chain rigidity is big; Gas permeability is poor; While is owing to the rigidity of polyimide molecule chain itself, and intermolecular strong interaction, makes medium-sized polyimides until neither fusion of decomposition temperature; Also do not dissolve, the result is difficult to process film forming.Improve dissolubility and machinability, and to keep its excellent properties be one of focus of research at present.Discover; The molecular weight that increases polyimide gas separating film can make performances such as its intensity and malleable be improved; Though what use now is that molecular weight has reached 50000 polyimides, molecular weight greater than 50000 polyimide gas separating film will tool application prospect widely.Therefore, how to prepare a kind of resolvability that has, molecular weight is high, and film forming and permeance property are good, and preparation technology is simple, and cost is low, is easy to industrialization, and polyimide gas separating film easy to utilize then is the current problem of being badly in need of solution in the art.
Summary of the invention
It is strong to the purpose of this invention is to provide a kind of dissolubility, and molecular weight is high, and film forming and permeance property are good, preparation technology is simple, cost is low, be easy to industrialization polyimide gas separation membrane with high molecular weight easy to utilize and preparation method.
In order to achieve the above object; The present invention adopts following technical scheme: a kind of polyimide gas separation membrane with high molecular weight; Be characterized in: by aromatic diamines and aromatic dianhydride example 1: 1.0-1 in molar ratio: 1.3, be dissolved in the polar solvent, forming mass concentration is the solution of 1%-40%; At first the prepared in reaction polyamic acid solution is processed polyimide gas separation membrane with high molecular weight again behind system film and demoulding.
Above-mentioned said polyimide gas separation membrane with high molecular weight has weight average molecular weight and is higher than 80000.
Above-mentioned said aromatic diamines comprises: 2; Two (the 3-amino-4-hydroxy phenyl) HFC-236fas (Bis-AP-AF), 3 of 2-; 3 '-dimethyl-4; 4 '-diphenylmethane diamine (DMMDA), 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas (BAHFP), 4 of 2-, 4 '-diaminodiphenyl ether (ODA) etc.
Above-mentioned said aromatic dianhydride comprises: 3,3 ', 4, and 4 '-benzophenone tetracarboxylic dianhydride (BTDA), 3,3 '; 4,4 '-triphen diether tetracarboxylic dianhydride (HQDPA), 4,4 '-hexafluoroisopropyli,ene-phthalic anhydride (6FDA), 3,3 ', 4; 4 '-diphenyl ether tetracarboxylic dianhydride (ODPA), 3,3 ', 4,4 '-BPDA (BPDA), 1,2 '; 4,5 '-pyromellitic dianhydride (PMDA), 3,3 ', 4,4 '-diphenyl sulphone (DPS) tetracarboxylic dianhydride (DSDA) etc.
Above-mentioned said polar solvent comprises: N-methyl pyrrolidone, N, N-dimethylacetylamide, N, dinethylformamide, phenol, cresols, parachlorophenol, 1,2,4-trichloro-benzene, o-dichlorohenzene, DAA and oxolane and carbinol mixture etc.
The preparation method of above-mentioned said polyimide gas separation membrane with high molecular weight comprises following processing step:
A. prepare polyamic acid solution
Under nitrogen or argon shield, described aromatic diamine monomers under agitation is dissolved in the described polar solvent, after dissolving finishes; Under-20 ℃-23 ℃; Add described aromatic dianhydride again, be reflected at lasting 2-24h under the continuous stirring, obtain polyamic acid solution;
B. prepare polyimide film
The hot-imide film forming; After above-mentioned polyamic acid solution is diluted to mass fraction and is 1-15%,, and the film forming glass plate placed fill the nitrogen baking oven and carry out hot-imide in glass plate top casting film forming; The hot-imide temperature is 60 ℃-400 ℃, and the time of hot-imide is 2h-48h;
Chemistry imidizate film forming; In above-mentioned polyamic acid solution, add dehydrating agent and carry out chemical imidizate, at-20 ℃-23 ℃ reaction 12-48h down, after after the reaction end it being diluted to mass fraction and being 1-15% with catalyst; In glass plate top casting film forming; And the film forming glass plate placed fill the nitrogen baking oven, under 100 ℃ of-400 ℃ of temperature, dried 4-48h;
C. polyimide film demoulding
The glass plate that will have polyimide film is cooled to room temperature, carries out the poach demoulding then, and the film of taking off from glass plate becomes the polyimide gas separation membrane with high molecular weight that thickness is 20-100 μ m.
The above-mentioned said aromatic dianhydride that adds again is the aromatic dianhydride monomer or is dissolved in the aromatic dianhydride solution in the said polar solvent.
Above-mentioned said dehydrating agent comprises: acetic anhydride, propionic andydride, valeric anhydride etc., consumption are 0.1-6 times of diamine monomer molal quantity; Said catalyst comprises: pyridine, triethylamine, isoquinolin etc., consumption are 0.1-8 times of diamine monomer molal quantity.
Because having adopted above-mentioned aromatic diamines, aromatic dianhydride is that raw material at first prepares polyamic acid, adopts hot-imide film forming or chemical imidizate film forming principle to prepare the process of polyimide gas separating film then, it is strong to make that the present invention has dissolubility; Molecular weight is high, good penetrability, stable performance; Film forming is good, and machine-shaping is easy, and preparation technology is simple; Cost is low, is easy to industrialization, can be widely used in CO in oil, the natural gas
2/ CH
4, CO
2/ H
2Separation, reached the purpose of invention.
The specific embodiment:
Below in conjunction with specific embodiment the present invention is described in further detail:
Embodiment 1:
The N that in mechanical agitator, thermometer, nitrogen are housed derive the dry four-hole boiling flask of pipe, adds 60mL; The N-dimethylacetylamide; Logical nitrogen protection under strong mechanical agitation, adds 2 of 21.98g (0.06mol); Two (the 3-amino-4-hydroxy phenyl) HFC-236fas (Bis-AP-AF) of 2-are stirred to fully and are cooled to after the dissolving-5-0 ℃; Then, with 19.62g (1.015 * 0.06mol) 3,3 '; 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is dissolved in the N of 60mL, in the N-dimethylacetylamide; Fully slowly join again in the above-mentioned four-hole boiling flask reactor after the dissolving ,-5-0 ℃ following reaction 2-6h, obtain polyamic acid solution; The polyamic acid that is synthesized is used N, and the N-dimethylacetylamide directly is diluted to the solution that mass fraction is 5-10%, is tiled in equably then on the clean glass plate; Filling the heating rate of nitrogen baking oven, carrying out hot-imide at 60 ℃ of constant temperature 8h, 120 ℃ of constant temperature 1h, 150 ℃ of constant temperature 1h, 200 ℃ of constant temperature 2h, 250 ℃ of constant temperature 1-3h, 275 ℃ of constant temperature 1-3h successively with 1 ℃/min; The glass plate that has polyimide film after hot-imide handled is cooled to room temperature, poach demoulding then, and promptly making thickness is that 60 μ m weight average molecular weight are 110600 polyimide gas separation membrane with high molecular weight.
Embodiment 2:
Present embodiment and specific embodiment 1 are different is that the reaction temperature of synthesizing polyamides acid is 0-5 ℃.Other is identical with specific embodiment 1; Finally making thickness is that 43 μ m weight average molecular weight are 109800 polyimide gas separation membrane with high molecular weight.
Embodiment 3:
That present embodiment and specific embodiment 1 are different is the N that in four-hole boiling flask, adds 50mL, N-dimethylacetylamide and with 3, and 3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) is dissolved in the N of 50mL, in the N-dimethylacetylamide.Other is identical with specific embodiment 1; Finally making thickness is that 57 μ m weight average molecular weight are 98300 polyimide gas separation membrane with high molecular weight.
Embodiment 4:
The N that in mechanical agitator, thermometer, argon gas are housed derive the dry four-hole boiling flask of pipe, adds 150mL; The N-dimethylacetylamide; Logical argon shield under strong mechanical agitation, adds 2 of 21.98g (0.06mol); Two (the 3-amino-4-hydroxy phenyl) HFC-236fas (Bis-AP-AF) of 2-are stirred to fully and are cooled to 0-5 ℃ after the dissolving; Then with 19.62g (1.015 * 0.06mol) 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA) slowly joins in the above-mentioned four-hole boiling flask reactor, at 0-5 ℃ of following reaction 3-8h, obtains polyamic acid solution; Add 10.21g (0.10mol) acetic anhydride more respectively and 2.37g (0.03mol) pyridine carries out chemical imidizate; Obtain polyimide solution behind the reaction 12-24h under the room temperature; Prepared polyimide solution is used N; The N-dimethylacetylamide directly is diluted to the solution that mass fraction is 5-10%, is tiled in equably then on the clean glass plate; With the heating rate of 1 ℃/min, successively at 140-150 ℃ of following constant temperature 4-6h, 270-280 ℃ of following constant temperature 12-24h carries out dried in filling the nitrogen baking oven; The glass plate that has polyimide film after the dried is cooled to room temperature, poach demoulding then, promptly making thickness is that 45 μ m weight average molecular weight are 101300 polyimide gas separation membrane with high molecular weight.
Embodiment 5:
What present embodiment and specific embodiment 4 were different is logical nitrogen protection.Other is identical with specific embodiment 1; Finally making thickness is that 38 μ m weight average molecular weight are 100200 polyimide gas separation membrane with high molecular weight.
Embodiment 6:
The N-methyl pyrrolidone that in mechanical agitator, thermometer, nitrogen are housed derive the dry four-hole boiling flask of pipe, adds 50mL; Logical nitrogen protection; Under strong mechanical agitation, add 3 of 11.30g (0.05mol), 3 '-dimethyl-4; 4 '-diphenylmethane diamine (DMMDA) is stirred to fully and is cooled to 0-5 ℃ after the dissolving; Then, with 20.40g (1.015 * 0.05mol) 3,3 '; 4,4 '-triphen diether tetracarboxylic dianhydride (HQDPA) is dissolved in the N-methyl pyrrolidone of 50mL, fully slowly joins in the above-mentioned four-hole boiling flask reactor after the dissolving again; React 12-18h down at 0-5 ℃, obtain polyamic acid solution; Add 25.5g (0.25mol) acetic anhydride more respectively and 23.3g (0.23mol) triethylamine carries out chemical imidizate; Obtain polyimide solution behind the reaction 12-36h under the room temperature; Using the N-methyl pyrrolidone directly to be diluted to mass fraction prepared polyimide solution is 10% solution, is tiled in equably then on the clean glass plate; With the heating rate of 1 ℃/min, successively at 120-150 ℃ of following constant temperature 4-8h, 250-400 ℃ of following constant temperature 1-24h carries out dried in filling the nitrogen baking oven; The glass plate that has polyimide film after the dried is cooled to room temperature, poach demoulding then, promptly making thickness is that 62 μ m weight average molecular weight are 91500 polyimide gas separation membrane with high molecular weight.
Claims (4)
1. the preparation method of a polyimide gas separation membrane with high molecular weight; By aromatic diamines and aromatic dianhydride example 1: 1.0-1: 1.3 in molar ratio; Be dissolved in the polar solvent, forming mass concentration is the solution of 1%-40%, at first the prepared in reaction polyamic acid solution; Behind hot-imide film forming or chemical imidizate film build method system film, behind demoulding, process the polyimide gas separation membrane with high molecular weight that weight average molecular weight is 80000-110600 again;
Aromatic diamines is selected from: 2, and two [the 3 amino-4-hydroxy phenyl] HFC-236fas, 3 of 2-, 3 '-dimethyl-4,4 '-diphenylmethane diamine, 2, two [4-(4-amino-benzene oxygen) phenyl] HFC-236fas, 4 of 2-, 4 '-diaminodiphenyl ether; Aromatic dianhydride is selected from: 3,3 ', 4, and 4 '-benzophenone tetracarboxylic dianhydride, 3,3 '; 4,4 '-triphen diether tetracarboxylic dianhydride, 4,4 '-hexafluoroisopropyli,ene-phthalic anhydride, 3,3 ', 4; 4 '-diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 '-BPDA, 1,2 '; 4,5 '-pyromellitic dianhydride, 3,3 ', 4,4 '-diphenyl sulphone (DPS) tetracarboxylic dianhydride;
Hot-imide becomes the processing step of embrane method following:
A. prepare polyamic acid solution
Under nitrogen or argon shield, described aromatic diamine monomers under agitation is dissolved in the described polar solvent, after dissolving finishes; Under-20 ℃-23 ℃; Add described aromatic dianhydride again, be reflected at lasting 2-24h under the continuous stirring, obtain polyamic acid solution;
B. prepare polyimide film
After above-mentioned polyamic acid solution is diluted to mass fraction and is 1-15%, in glass plate top casting film forming, and the film forming glass plate placed fill the nitrogen baking oven and carry out hot-imide, the hot-imide temperature is 60 ℃-400 ℃, and the time of hot-imide is 2h-48h;
C. polyimide film demoulding
The glass plate that will have polyimide film is cooled to room temperature, carries out the poach demoulding then, and the film of taking off from glass plate becomes the polyimide gas separation membrane with high molecular weight that thickness is 20-100 μ m;
Chemistry imidizate film forming becomes the processing step of embrane method following:
A. prepare polyamic acid solution
Under nitrogen or argon shield, described aromatic diamine monomers under agitation is dissolved in the described polar solvent, after dissolving finishes; Under-20 ℃-23 ℃; Add described aromatic dianhydride again, be reflected at lasting 2-24h under the continuous stirring, obtain polyamic acid solution;
B. prepare polyimide film
Adding dehydrating agent and catalyst carry out chemical imidizate in above-mentioned polyamic acid solution; React 12-48h down at-20 ℃-23 ℃; After after reaction finishes it being diluted to mass fraction and being 1-15%,, and the film forming glass plate placed fill the nitrogen baking oven in glass plate top casting film forming; Under 100 ℃ of-400 ℃ of temperature, dried 4-48h;
C. polyimide film demoulding
The glass plate that will have polyimide film is cooled to room temperature, carries out the poach demoulding then, and the film of taking off from glass plate becomes the polyimide gas separation membrane with high molecular weight that thickness is 20-100 μ m.
2. according to the preparation method of the said polyimide gas separating film of claim 1; It is characterized in that: said polar solvent is selected from: N-methyl pyrrolidone, N; N-dimethylacetylamide, N; Dinethylformamide, phenol, cresols, parachlorophenol, 1,2,4-trichloro-benzene, o-dichlorohenzene, DAA and oxolane and carbinol mixture.
3. according to the preparation method of the said polyimide gas separating film of claim 1, it is characterized in that: to add described aromatic dianhydride be the aromatic dianhydride monomer or be dissolved in the aromatic dianhydride solution in the said polar solvent.
4. according to the preparation method of the said polyimide gas separating film of claim 1, it is characterized in that: said dehydrating agent is selected from: acetic anhydride, propionic andydride, valeric anhydride, consumption are 0.1-6 times of diamine monomer molal quantity; Said catalyst is selected from: pyridine, triethylamine, isoquinolin, consumption are 0.1-8 times of diamine monomer molal quantity.
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| CN102824857A (en) * | 2011-06-14 | 2012-12-19 | 北京航空航天大学 | Preparation method of gas separation carbon membrane |
| CN102580580B (en) * | 2012-02-27 | 2014-05-28 | 北京市射线应用研究中心 | Polyimide gas separation membrane and preparation method thereof |
| CN102716680B (en) * | 2012-06-05 | 2014-05-07 | 中国科学院化学研究所 | Polyamide microporous membrane and preparation method thereof |
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| CN110433672B (en) * | 2018-05-03 | 2021-11-19 | 李保军 | Non-coplanar polyimide gas separation membrane with large steric hindrance and preparation method thereof |
| CN111214969A (en) * | 2018-11-23 | 2020-06-02 | 中国科学院大连化学物理研究所 | Polyether-co-polyimide film, preparation and application thereof |
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| CN113813800A (en) * | 2021-10-19 | 2021-12-21 | 中国科学院山西煤炭化学研究所 | Preparation of polyimide membrane containing chlorine polar group and gas separation application thereof |
| CN114699928A (en) * | 2022-04-18 | 2022-07-05 | 西安交通大学 | Mixed matrix membrane preparation method based on in-situ polymerization |
| CN115160565A (en) * | 2022-06-22 | 2022-10-11 | 浙江工业大学 | Polyimide film material containing sulfonyl structure between imide rings and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1462291A (en) * | 2001-02-27 | 2003-12-17 | 钟渊化学工业株式会社 | Polyimide film and process for producing the same |
| CN1587298A (en) * | 2004-08-13 | 2005-03-02 | 上海华谊（集团）公司 | Process for preparing soluble polyimide |
| CN101423607A (en) * | 2008-11-12 | 2009-05-06 | 吉林大学 | Thermoplastic poly(ether-ether-ketone) type polyimide and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1462291A (en) * | 2001-02-27 | 2003-12-17 | 钟渊化学工业株式会社 | Polyimide film and process for producing the same |
| CN1587298A (en) * | 2004-08-13 | 2005-03-02 | 上海华谊（集团）公司 | Process for preparing soluble polyimide |
| CN101423607A (en) * | 2008-11-12 | 2009-05-06 | 吉林大学 | Thermoplastic poly(ether-ether-ketone) type polyimide and preparation method thereof |
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