CN113731198B - Preparation method of high-selectivity polyimide gas separation membrane - Google Patents
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 44
- 239000004642 Polyimide Substances 0.000 title claims abstract description 42
- 239000012528 membrane Substances 0.000 title claims abstract description 29
- 238000000926 separation method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000178 monomer Substances 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 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 description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012024 dehydrating agents Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- RKFCDGOVCBYSEW-AUUKWEANSA-N tmeg Chemical compound COC=1C(OC)=CC(C(OC(C=2OC)=C34)=O)=C3C=1OC(=O)C4=CC=2O[C@@H]1O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1O RKFCDGOVCBYSEW-AUUKWEANSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BWWHTIHDQBHTHP-UHFFFAOYSA-N 2-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=CC=C1C(Cl)=O BWWHTIHDQBHTHP-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 7
- 239000007788 liquid Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 6
- 150000004985 diamines Chemical class 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 125000006159 dianhydride group Chemical group 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 101100391241 Antheraea mylitta fpi-1 gene Proteins 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 229920002301 cellulose acetate Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- MSTZGVRUOMBULC-UHFFFAOYSA-N 2-amino-4-[2-(3-amino-4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phenol Chemical compound C1=C(O)C(N)=CC(C(C=2C=C(N)C(O)=CC=2)(C(F)(F)F)C(F)(F)F)=C1 MSTZGVRUOMBULC-UHFFFAOYSA-N 0.000 description 1
- NMRDKGOPQYFYTD-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-nitrophenyl)propan-2-yl]-2-nitrophenol Chemical compound C1=C([N+]([O-])=O)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C([N+]([O-])=O)=C1 NMRDKGOPQYFYTD-UHFFFAOYSA-N 0.000 description 1
- SKDHHIUENRGTHK-UHFFFAOYSA-N 4-nitrobenzoyl chloride Chemical compound [O-][N+](=O)C1=CC=C(C(Cl)=O)C=C1 SKDHHIUENRGTHK-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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
-
- 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)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a preparation method of a high-selectivity polyimide gas separation membrane, which comprises the steps of firstly synthesizing a diamine monomer 6FDAP containing trifluoromethyl and hydroxyl simultaneously through two-step organic synthesis, and then synthesizing three kinds of polyimide with different dianhydrides through a chemical imidization method. And coating the prepared polyimide solution on a template, and drying to obtain the 6 FDAP-based polyimide film. The preparation method of the invention synthesizes diamine monomer 6FDAP containing trifluoromethyl and hydroxyl through chemical synthesis, then synthesizes 6 FDAP-based polyimide through chemical imidization, and the synthesized polyimide not only has excellent thermal stability due to a large amount of trifluoromethyl and hydroxyl, but also endows the polyimide with CO resistance 2 /CH 4 Has high selectivity and can be used for CO 2 The method has the advantages of simple process, low cost, environmental protection and easy industrialization in the aspects of trapping and the like.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a preparation method of a high-selectivity polyimide gas separation membrane.
Background
In recent years, due to CO 2 Greenhouse effect, global warming, the problems of glacier melting and the like seriously destroy the ecological environment of the earth on which people depend to live. Thus, CO 2 The excessive emissions of (a) have become a problem that humans have to face and are urgently addressed.
Membrane separation is the current industrial separation and enrichment of natural gas and CO in flue gas 2 Is an emerging method of (a). The membrane separation materials commonly used mainly include high polymer materials such as Cellulose Acetate (CA), polyethyleneimine (PEI) and Polyimide (PI). Polyimide is a polymer material formed by connecting imide rings, and has been paid attention to by many researchers because of the advantages of excellent thermal stability, strong hydrophobicity, stable chemical properties and the like. The fluorine element is a very magic element, and the introduction of the fluorine element into the polyimide not only can enhance the thermal stability, the light transmittance and the hydrophobic property of the polyimide, but also can be matched with polar gas CO 2 Generating four-pole-dipole interaction, improving CO 2 /CH 4 Is selected from the group consisting of (1). However, so far, due to "Trade-off"The effect, polyimide membranes have not achieved very desirable results in the separation of carbon dioxide. Thus, a class of para-CO was developed 2 The fluorine-containing polyimide film with higher selectivity has good application prospect.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for preparing a polyimide gas separation membrane with high selectivity, which uses trifluoromethyl and hydroxyl groups in 6 FDAP-based polyimide to react with CO 2 The property of interaction effectively promotes CO 2 /CH 4 And the selectivity is high, and the 6 FDAP-based polyimide contains a large amount of fluorine elements, so that the polyimide has excellent thermal stability, hydrophobicity and light transmittance.
In order to achieve the above purpose, the technical scheme of the invention is realized as follows:
a preparation method of a high-selectivity polyimide gas separation membrane comprises the following steps:
(1) Mixing 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (abbreviated as 6 FAP) with NMP, heating to 40-70 ℃ to obtain a pale yellow solution A, mixing nitrobenzoyl chloride with toluene to obtain a solution B, slowly dropwise adding the solution B into the solution A at 50-70 ℃, reacting for 1-5 hours at 50-80 ℃, preferably reacting for 3 hours at 60 ℃, mixing the reaction solution with methanol, reducing the temperature to room temperature, separating out a large amount of white solid, separating out the solid, washing three times with methanol, vacuum drying at 90 ℃ for 12 hours to obtain white solid 2, 2-bis (3-nitro-4-hydroxyphenyl) hexafluoropropane (abbreviated as 6 FDNP), mixing 6FDNP with DMF, adding palladium carbon, reacting for 8-12 hours in a hydrogen atmosphere, mixing the reaction solution with deionized water, separating out the solid, washing, and drying to obtain the expected diamine monomer 6FDAP;
(2) Mixing dianhydride monomer and DMAC, dissolving, adding 6FDAP at 0-25 ℃, reacting for 8-24 hours at a temperature of 0-25 ℃, adding a dehydrating agent and a catalyst, continuously reacting for 8-12 hours, mixing reaction liquid and ethanol, separating out solid, washing for 10-18 hours by using ethanol, and drying for 20-30 hours at 120-200 ℃ to obtain 6 FDAP-based polyimide;
(3) Mixing 6 FDAP-based polyimide with DMAC to obtain a casting solution, smearing the casting solution on a template, volatilizing a solvent to obtain a prefabricated membrane, and carrying out high-temperature heat treatment on the prefabricated membrane to obtain the required separation membrane.
Further, the dianhydride monomer includes at least one of 6FDA, TA-TFMB and TMEG.
Further, the dehydrating agent in the step (2) is acetic anhydride.
Further, the catalyst in the step (2) is triethylamine.
Further, the solid content of the casting solution is 5-8wt%; preferably 7wt%.
Further, the template is a polytetrafluoroethylene template.
Further, the method of the high-temperature heat treatment in the step (3) is to dry the prefabricated film for 24 hours at 100-150 ℃.
Compared with the prior art, the preparation method of the high-selectivity polyimide gas separation membrane has the following advantages:
the preparation method of the invention synthesizes diamine monomer 6FDAP containing trifluoromethyl and hydroxyl through chemical synthesis, then synthesizes 6 FDAP-based polyimide through chemical imidization, and the synthesized polyimide not only has excellent thermal stability due to a large amount of trifluoromethyl and hydroxyl, but also endows the polyimide with CO resistance 2 /CH 4 Has high selectivity and can be used for CO 2 The method has the advantages of simple process, low cost, environmental protection and easy industrialization in the aspects of trapping and the like.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. In the drawings:
FIG. 1 is an XRD pattern of a 6 FDAP-based polyimide prepared in examples 1-3 of the present invention;
FIG. 2 shows a 6FDAP according to an embodiment of the invention 1 HNMR diagram;
FIG. 3 is a schematic diagram of a connection structure of a high molecular polymer gas separation performance test device according to an embodiment of the present invention;
FIG. 4 is a graph showing the CO content of the separation membranes prepared in examples 1 to 3 of the present invention 2 /CH 4 Gas separation diagram.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention pertains. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified.
The present invention will be described in detail with reference to the following examples and drawings.
Example 1
Synthesis of (1) 6FDNP
6g of 6FAP was weighed out and added to 24mL of NMP and heated to 60℃to form a pale yellow solution, designated solution A. Then, 6.62g of p-nitrobenzoyl chloride was weighed out and dissolved in 7mL of toluene and designated as solution B. Solution A was maintained at 60℃and solution B was slowly added dropwise to solution A. The reaction was carried out for 3 hours while maintaining the temperature, 50mL of a methanol solution was added to the reaction mixture, and the temperature was lowered to room temperature, whereby a large amount of white solid was precipitated. After washing the white solid three times with methanol, the white solid 6FDNP,10g, was collected after drying at 90℃for 12h in vacuo.
(II) Synthesis of 6FDAP
Dissolving the synthesized 6FDNP in 30mL of DMF, adding 0.1g of Pd/C, introducing hydrogen, reacting for 12 hours at 30 ℃, dropwise adding 50mL of deionized water into the reaction solution, precipitating a large amount of white solid, filtering, washing with methanol three times, drying at 90 ℃ for 12 hours to obtain 9g of white solid 6FDAP, and using 1 HNMR determines that the structure is correct as shown in fig. 2.
Synthesis of (III) 6 FDAP-based polyimide
2g of 6FDA is dissolved in 10mL of DMAC, the solution is colorless and transparent, the reaction temperature is reduced to 0 ℃, 2.72g of prepared 6FDAP is weighed and added into the reaction solution, after 2h of reaction, the temperature is raised to 25 ℃, and the reaction is continued for 10h. To the reaction solution, 0.8mL of triethylamine and 2.7mL of acetic anhydride were added, and the solution became viscous soon, and the reaction was continued at room temperature for 12 hours. The reaction solution was poured into 300mL of ethanol, a large amount of white filaments were precipitated, and the solution was filtered and washed with ethanol for 12 hours. The washed polyimide was dried in vacuo at 150℃for 24 hours to give a white 6 FDAP-based polyimide, 4g, designated FPI-1.
(IV) Synthesis of separation Membrane
Dissolving 0.5g of FPI-1 in 7mL of DMAC, carrying out ultrasonic defoaming, uniformly coating on a polytetrafluoroethylene plate, placing in an oven, drying at 60 ℃ for 8 hours, setting, falling off, and carrying out vacuum drying at 150 ℃ for 24 hours to obtain the 6 FDAP-based high CO 2 /CH 4 A selective polyimide gas separation membrane.
Example 2
The difference from example 1 is that 6FDA was replaced with TA-TFMB in step (III) to give a white 6 FDAP-based polyimide, designated FPI-2, and the other steps were the same as in example 1.
Example 3
The difference from example 1 is that 6FDA was replaced with TMEG in step (III) to give a white 6 FDAP-based polyimide designated FPI-3, and the other steps were the same as in example 1.
CO was performed on the separation membranes obtained in examples 1 to 3 and three commercially available polyimide membranes 2 /CH 4 The gas separation performance test is carried out, the connection structure of the gas separation performance test equipment is shown in fig. 4, wherein F1-10 are valves, and the specific experimental steps are as follows:
(1) The separation membranes prepared in examples 1 to 3 and three commercially available polyimide membranes (respectively5218. 6FDA-ODA and P84), respectively filling the membrane tanks, starting a vacuum pump, F3, F6 and F7, then starting F4 and F5, and then slowly starting F8 to perform membrane tank up and down and air extraction, wherein F1 and F2 are in a closed state; when the vacuum degree reaches 3.0X10 -2 The test can be carried out when the Torror is lower;
(2) Firstly, F4 and F8 are sequentially closed, then F1 is opened to be filled with test gas with certain pressure, F2 is repeatedly opened to replace the gas for three times, after the sample injection pressure is adjusted, F3 (according to the requirement of the test gas), F6, F7 and a vacuum pump are closed, F4 is opened to click "start" to start data acquisition, and at the moment, F1 and F2 are still in a closed state;
(3) After the test is finished, the vacuum pumps F3, F6 and F7 are opened, the pressure reducing valves are closed, the F1 and F2 are closed after the sample injection pipelines are emptied by opening the F1 and F2, and then the F8 is slowly opened and simultaneously air is exhausted.
And the permeability coefficient P of the gas can be calculated by testing the curve of the change of the gas pressure of the upper membrane pool along with the time. Three separation membranes prepared in examples 1-3 and commercially available common polyimide membrane pair CO 2 /CH 4 The separation performance is shown in Table 1 and FIG. 4. As can be seen from the analysis of Table 1, according to the technical scheme provided by the invention, the obtained 6 FDAP-based polyimide has higher CO than common polyimide 2 /CH 4 Selectivity.
TABLE 1 results of Performance experiments
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (8)
1. The preparation method of the high-selectivity polyimide gas separation membrane is characterized by comprising the following steps of:
(1) Mixing 6FAP with NMP to obtain a solution A, mixing nitrobenzoyl chloride with toluene to obtain a solution B, slowly dripping the solution B into the solution A at 50-70 ℃, reacting for 1-5 hours at 50-80 ℃, mixing the reaction solution with methanol, separating out solid, washing, drying to obtain 6FDNP, mixing 6FDNP with DMF, adding palladium carbon, reacting for 8-12 hours in a hydrogen atmosphere, mixing the reaction solution with deionized water, separating out solid, washing, drying to obtain 6FDAP;
(2) Mixing dianhydride monomer, DMAC and 6FDAP at 0-25 ℃, reacting for 8-24 hours at a temperature of 0-25 ℃, adding a dehydrating agent and a catalyst, continuously reacting for 8-12 hours, mixing the reaction solution with ethanol, separating out solid, washing and drying to obtain 6 FDAP-based polyimide;
(3) Mixing 6 FDAP-based polyimide with DMAC to obtain a casting solution, smearing the casting solution on a template, volatilizing a solvent to obtain a prefabricated membrane, and carrying out high-temperature heat treatment on the prefabricated membrane to obtain the required separation membrane.
2. The method of manufacturing according to claim 1, characterized in that: the dianhydride monomer comprises at least one of 6FDA, TA-TFMB and TMEG.
3. The method of manufacturing according to claim 1, characterized in that: the dehydrating agent in the step (2) is acetic anhydride.
4. The method of manufacturing according to claim 1, characterized in that: the catalyst in the step (2) is triethylamine.
5. The method of manufacturing according to claim 1, characterized in that: and (2) mixing the reaction solution with ethanol, separating out solid, washing with ethanol for 10-18h, and drying at 120-200 ℃ for 20-30h to obtain the 6 FDAP-based polyimide.
6. The method of manufacturing according to claim 1, characterized in that: the solid content of the casting film liquid is 5-8wt%.
7. The method of manufacturing according to claim 1, characterized in that: the template is a polytetrafluoroethylene template.
8. The method of manufacturing according to claim 1, characterized in that: the high-temperature heat treatment method in the step (3) is to dry the prefabricated film for 24 hours at 100-150 ℃.
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| KR20020052551A (en) * | 2000-12-26 | 2002-07-04 | 김충섭 | Fluorine-based polyimide composite membrane for gas separation |
| CN103846023A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院大连化学物理研究所 | Copolymerization polyimide gas separation membrane material, preparation method and application of copolymerization polyimide gas separation membrane material |
| US9233344B1 (en) * | 2014-09-29 | 2016-01-12 | Uop Llc | High selectivity polyimide membrane for natural gas upgrading and hydrogen purification |
| CN107376672A (en) * | 2017-06-23 | 2017-11-24 | 江南大学 | A kind of environment-friendly preparation method thereof of polyimide gas separating film |
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| CN111770951A (en) * | 2019-02-01 | 2020-10-13 | 胜高科技股份有限公司 | Polyimide compound and molded article comprising same |
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