CN115725076A - Block copolymer, preparation method thereof and application thereof in gas separation membrane - Google Patents
Block copolymer, preparation method thereof and application thereof in gas separation membrane Download PDFInfo
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- CN115725076A CN115725076A CN202111022217.9A CN202111022217A CN115725076A CN 115725076 A CN115725076 A CN 115725076A CN 202111022217 A CN202111022217 A CN 202111022217A CN 115725076 A CN115725076 A CN 115725076A
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- 239000012528 membrane Substances 0.000 title claims abstract description 83
- 238000000926 separation method Methods 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 108
- 150000004985 diamines Chemical class 0.000 claims abstract description 56
- 238000010438 heat treatment Methods 0.000 claims abstract description 46
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000012298 atmosphere Substances 0.000 claims abstract description 36
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 229920001721 polyimide Polymers 0.000 claims description 82
- 239000004642 Polyimide Substances 0.000 claims description 80
- 238000001035 drying Methods 0.000 claims description 55
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 46
- 239000011521 glass Substances 0.000 claims description 42
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 230000001590 oxidative effect Effects 0.000 claims description 21
- 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 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 15
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- -1 dianhydride a Chemical class 0.000 claims description 9
- 229920005575 poly(amic acid) Polymers 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- FLDSMVTWEZKONL-AWEZNQCLSA-N 5,5-dimethyl-N-[(3S)-5-methyl-4-oxo-2,3-dihydro-1,5-benzoxazepin-3-yl]-1,4,7,8-tetrahydrooxepino[4,5-c]pyrazole-3-carboxamide Chemical compound CC1(CC2=C(NN=C2C(=O)N[C@@H]2C(N(C3=C(OC2)C=CC=C3)C)=O)CCO1)C FLDSMVTWEZKONL-AWEZNQCLSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- 238000005266 casting Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229920006254 polymer film Polymers 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 230000000379 polymerizing effect Effects 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000007606 doctor blade method Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000006210 lotion Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004973 liquid crystal related substance Substances 0.000 claims 1
- 238000012545 processing Methods 0.000 claims 1
- 238000007790 scraping Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000000178 monomer Substances 0.000 abstract description 6
- 229920005597 polymer membrane Polymers 0.000 abstract description 2
- 239000007787 solid Substances 0.000 description 29
- PISLZQACAJMAIO-UHFFFAOYSA-N 2,4-diethyl-6-methylbenzene-1,3-diamine Chemical compound CCC1=CC(C)=C(N)C(CC)=C1N PISLZQACAJMAIO-UHFFFAOYSA-N 0.000 description 26
- 150000008064 anhydrides Chemical class 0.000 description 17
- 230000035699 permeability Effects 0.000 description 11
- 238000010992 reflux Methods 0.000 description 9
- 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 7
- 238000001704 evaporation Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000010926 purge Methods 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000012466 permeate Substances 0.000 description 4
- WVFONJOODJOYPV-UHFFFAOYSA-N 6,6-diamino-3-phenylcyclohexa-2,4-diene-1,1-diol Chemical compound OC1(O)C(N)(N)C=CC(C=2C=CC=CC=2)=C1 WVFONJOODJOYPV-UHFFFAOYSA-N 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000000355 1,3-benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- QHHKLPCQTTWFSS-UHFFFAOYSA-N 5-[2-(1,3-dioxo-2-benzofuran-5-yl)-1,1,1,3,3,3-hexafluoropropan-2-yl]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)(C(F)(F)F)C(F)(F)F)=C1 QHHKLPCQTTWFSS-UHFFFAOYSA-N 0.000 description 1
- 238000000692 Student's t-test Methods 0.000 description 1
- RFXQKWLYZGJSHE-UHFFFAOYSA-N [He].O=C=O Chemical compound [He].O=C=O RFXQKWLYZGJSHE-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- NNEUCPRHEGXIDG-UHFFFAOYSA-N helium;methane Chemical compound [He].C NNEUCPRHEGXIDG-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a block copolymer and a preparation method thereof, and application of the block copolymer in a gas separation membrane, including the block copolymer and the preparation method thereof, and a polymer membrane prepared by using the block copolymer. The gas separation membrane with excellent gas separation performance is obtained by adjusting the block length, diamine proportion, heat treatment temperature, time and atmosphere of the block copolymer and performing heat treatment in a specific oxygen-containing atmosphere, the additional cost caused by using high-purity nitrogen is avoided, and meanwhile, commercial reaction monomers are adopted by changing the source of the reaction monomers, so that the preparation cost is effectively reduced, and the preparation method has great guiding significance for the preparation of the gas separation membrane.
Description
Technical Field
The invention belongs to the field of preparation of gas separation membranes, and particularly relates to a block copolymer, a preparation method and application thereof, and a polymer membrane with improved performance prepared by using the block copolymer.
Background
Polyimide resin is a polymer having a mainly amorphous structure, and exhibits excellent thermal stability, corrosion resistance, high mechanical strength due to its rigid structure. Therefore, the method is expected to have great development prospect in the field of gas membrane separation.
The polyimide material containing ortho hydroxyl group reacts at 350-450 ℃ in the inert gas atmosphere to generate a benzoxazole structure, and meanwhile, the gas permeability coefficient is greatly increased. However, in practice, it is difficult and expensive to obtain a high purity inert atmosphere. Therefore, the use of the inert gas containing a certain amount of oxygen can effectively reduce the cost.
At the same time, we have surprisingly found that the use of a hydroxyl-containing block polyimide of a specific composition by heat treatment in the presence of a certain amount of oxygen can achieve excellent gas separation performance while effectively reducing costs, particularly in the separation of hydrogen methane, hydrogen carbon dioxide, helium methane, helium carbon dioxide.
Disclosure of Invention
The preparation method comprises the following two steps of (1) preparing a block polyimide material, (2) preparing a block polyimide flat membrane, and (3) preparing a thermal oxidation hydroxyl-containing block polyimide gas separation membrane in a specific oxygen-containing atmosphere. Surprisingly, the block polyimide material containing the ortho-hydroxyl group provided by the invention is used for preparing the block polyimide film containing the ortho-hydroxyl group, and the excellent gas separation performance can be obtained by performing thermal oxidation treatment in an atmosphere with a certain oxygen content, so that the block polyimide material has great guiding significance for preparing the gas separation film.
According to one aspect of the present application, there is provided a block copolymer,
the structural formula of the block copolymer is shown as a formula I:
the block copolymer comprises a block A represented by a formula II and a block B represented by a formula III;
wherein the average polymerization degree m of the block A is 1-100;
the average polymerization degree n of the block B is 1-100;
R 1 is selected from R 1a 、R 1b 、R 1c 、R 1d 、R 1e 、R 1f 、R 1g One of (1);
R 2 is selected from R 2a 、R 2b 、R 2c 、R 2d 、R 2e 、R 2f One of (1);
R 3 is selected from R 3a Or R 3b One of the above two methods;
wherein L is 1 ，L 2 ，L 3 ，L 4 Independently selected from-H, -F, -Cl, -Br, -I, -CF 3 ，-CCl 3 ，-CBr 3 ，-CI 3 ，-CH 3 ，-C 2 H 5 ，-NO 2 -CN, -COOH.
Said R is 3 Middle L 1 ，L 2 ，L 3 ，L 4 In which at most two are-CH 3 ；
The block A is obtained by polymerizing dianhydride a and diamine b;
the block B is obtained by polymerizing dianhydride a and diamine c;
the structure of dianhydride a is shown as a; the structure of the diamine b is shown as b; the structure of the diamine c is shown as c;
according to another aspect of the present application, a method for preparing a block copolymer is provided, which is characterized in that a block A or a block B having a specific block length and an appropriate reactive end group is prepared, the block length (molecular weight) is 1000-80000 (average degree of polymerization is about 1-100, which is different according to the average degree of polymerization of the monomers used), and then other monomers are added to react with the block, so as to prepare a block polyimide material containing ortho-hydroxyl. The preparation method is selected from the method A or the method B;
wherein, the method X comprises the following steps:
(X1) mixing a raw material containing diamine and excessive dianhydride with a solvent I, stirring and reacting at 100-250 ℃ for 2-24 h, stopping heating and cooling to room temperature to obtain a solution a1;
(X2) mixing dianhydride and excessive diamine with the solution a1, reacting for 2-24 h at 100-250 ℃, adding a solvent, washing, and treating for 2-24 h at 100-250 ℃ to obtain the block polyimide material;
the method (Y) comprises:
(Y1) mixing a raw material containing diamine and excessive dianhydride with a solvent I at 0-5 ℃, stirring for 1-2 h, heating to 20-30 ℃, and stirring for 24-48h to obtain a solution b1;
(Y2) mixing dianhydride and excessive diamine with the solution b1 at the temperature of 0-5 ℃, stirring for 1-2 h, heating to 20-30 ℃, and stirring for 24-48h to obtain a block polyamic acid solution;
(Y3) adding a tertiary amine catalyst and acetic anhydride after the stirring in the step (Y2); stirring and reacting for 24-48h, pouring alcohol lotion, washing and drying, and treating for 2-24 h at 100-250 ℃ to obtain the block polyimide material.
In the step (X1) or the step (Y1), the molar ratio of the dianhydride to the diamine is 1-2;
preferably, the molar ratio of dianhydride to diamine is 1.1 to 1.9;
the solvent I is at least one selected from N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or m-cresol;
the diamine selected in the step (X1) is not a diamine b at the same time as the diamine selected in the step (X2), and is not a diamine c at the same time as the diamine selected in the step (X2);
the diamine selected in the step (Y1) is not a diamine b at the same time as the diamine selected in the step (Y2), and is not a diamine c at the same time as the diamine selected in the step (Y2);
in the method X or the method Y, the molar ratio of the diamine b to the diamine c is 0.01 to 100;
preferably, the molar ratio of diamine b to diamine c is from 0.1 to 10;
wherein the molar ratio of the total amount of diamine b and diamine c to the total amount of dianhydride in method X or Y is 0.8;
preferably, the molar ratio of the total amount of diamine b and diamine c to the total amount of dianhydride used in process X or Y is from 0.95 to 1.05;
in the step (X2) or the step (Y2), the washing is performed with a reagent selected from at least one of methanol, ethanol, and water;
in the step (Y3), the tertiary amine catalyst is at least one selected from pyridine and triethylene diamine;
the molar ratio of the tertiary amine catalyst to the total amount of acetic anhydride to dianhydride is 2:1:1.
according to another aspect of the present application, there is provided a flat sheet membrane whose raw material contains the block polyimide material described above or the block polyimide material or the block polyamic acid solution prepared according to the above-described preparation method.
According to another aspect of the present application, a method for preparing the flat membrane is provided.
The doctor blade method is selected from method (E) or method (F);
the method (E) comprises:
(E1) Coating the casting solution containing the block polyimide material on the surface of a substrate, drying, and stripping the obtained film from the substrate;
the substrate is selected from a glass plate or a polytetrafluoroethylene plate;
(E2) Continuously drying under vacuum or nitrogen atmosphere;
(E3) Heating to more than 200 ℃, and continuously drying in vacuum or nitrogen atmosphere;
wherein the drying temperature in the step (E1) is 40-100 ℃, and the drying time is 24-48 hours;
(E2) The drying temperature is 100-200 ℃, and the time is 12-24 hours;
preferably, the drying temperature in (E2) is 100 to 150 ℃;
preferably, the drying temperature in (E2) is 130 to 160 ℃;
e3 The drying temperature in the step (a) is 200-250 ℃ and the time is 1-4 hours;
the casting solution also contains a solvent II; the solvent II is at least one selected from N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or m-cresol;
the mass percentage concentration of the block polyimide material in the film casting liquid is 5-15 wt%.
The method (F) comprises:
(F1) Directly coating the block polyamic acid solution obtained in the step (Y2) in the method (Y) on the surface of a substrate, drying, and peeling the obtained film from the substrate;
the substrate is selected from a glass plate or a polytetrafluoroethylene plate;
(F2) Continuously drying under vacuum or nitrogen atmosphere;
(F3) Further heat treatment under nitrogen atmosphere;
wherein the drying temperature in the step (F1) is 40-100 ℃, and the drying time is 24-48 hours;
(F2) The drying temperature is 100-200 ℃, and the time is 12-24 hours;
(F3) The heat treatment temperature is 250-350 ℃, and the time is 1-12 hours;
preferably, the drying temperature in (F2) is 100 to 150 ℃;
preferably, the drying temperature in (F2) is 130 to 160 ℃.
According to another aspect of the present application, there is provided a gas separation membrane obtained by heating the above flat sheet membrane or the flat sheet membrane produced by the above method in an oxidizing atmosphere.
According to another aspect of the present application, there is provided a method for producing a gas separation membrane, comprising the method (G), the method (H), and the method (J);
wherein method (G) comprises the steps of: heating the flat membrane prepared by the preparation method in an oxidizing atmosphere to obtain the gas separation membrane;
the oxidizing atmosphere is a mixed atmosphere containing oxygen and inert gas; the inactive gas is at least one of nitrogen, helium, argon, krypton, xenon or carbon dioxide; the volume content of the oxygen is 0.1-50%.
The temperature of the treatment under the oxidizing atmosphere is 220-450 ℃, and the time is 1-5 hours;
preferably, the temperature of the treatment under the oxidizing atmosphere is 300 to 440 ℃.
Preferably, the temperature of the treatment under the oxidizing atmosphere is 350-440 ℃;
the method (H) comprises the following steps:
(H1) Heating the flat membrane prepared by the preparation method in an oxidizing atmosphere, and keeping the temperature for a certain time;
(H2) Reducing the temperature to a specific temperature at a certain speed in the same atmosphere, and keeping the temperature for a certain time to obtain the gas separation membrane;
the volume content of the oxygen is 0.1-50%.
The cooling rate is 0.1-10 ℃/min;
preferably, the constant temperature of the first stage is 420-440 ℃, and the constant temperature time is 1-2 hours;
preferably, the constant temperature of the second stage is 360-400 ℃, and the constant temperature time is 2-4 hours.
The method (J) comprises the steps of:
(J1) And heating the flat membrane prepared by the preparation method in an inert atmosphere, and keeping the temperature for a certain time.
(J2) Heating in an oxidizing atmosphere and keeping the temperature constant for a certain time to obtain the gas separation membrane;
in the inert atmosphere, at least one of nitrogen or argon is selected, and the oxygen content is less than 100 ppm.
In the oxidizing atmosphere, the volume content of oxygen is 0.1-50%.
Preferably, the constant temperature of the first stage is 400-440 ℃, and the constant temperature time is 1-4 hours;
preferably, the constant temperature of the second stage is 380-450 ℃, and the constant temperature time is 2-6 hours.
According to another aspect of the present application, there is provided a use of the above gas separation membrane in mixed gas separation.
The mixed gas is selected from H 2 And CH 4 Mixed gas of He and CH 4 Mixed gas, CO 2 And CH 4 Mixed gas of O 2 And N 2 Mixed gas of H 2 And N 2 Mixed gas, CO 2 And N 2 Mixed gas of H 2 And CO 2 At least one of the mixed gases;
the mixed gas is H 2 And CH 4 H of the polymer film in mixed gas 2 The selectivity of (A) is 10 to 300;
the mixed gas is He and CH 4 When mixed gas is adopted, the selectivity of He of the polymer film is 8-300;
the mixed gas is CO 2 And CH 4 CO of said polymer film when mixed with gas 2 The selectivity of (A) is 10 to 120.
The beneficial effects that this application can produce include:
the method adjusts the gas separation performance of the polyimide thermal oxidation gas separation membrane containing the ortho-position hydroxyl block by adjusting the block length of the block polyimide material, the diamine proportion, the heat treatment temperature, the time and the atmosphere, prepares the gas separation membrane with excellent separation performance, and simultaneously adopts commercial reaction monomers by changing the source of the reaction monomers, thereby effectively reducing the preparation cost.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Example 1 preparation of a Flat Membrane
Preparation of an oligomeric Block (Block molecular weight 3000, average degree of polymerization 3.87) in a 100mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen purge, 3.66g (10.0 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisasAPAF) were dissolved in 25g of m-cresol under a nitrogen atmosphere, 6.00g (13.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) were added stepwise to the solution, the solution was warmed to 180 ℃ under a nitrogen atmosphere, and stirred for 8 hours.
After the obtained solution was cooled to room temperature, 100g of m-cresol was added thereto, 5.94g (33.3 mmol) of diethyltoluenediamine (DETDA) and 13.24g (29.8 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride were successively added, and then the solution was heated to 180 ℃ under a nitrogen atmosphere and stirred for 8 hours. Then according to the condition of evaporating the solvent, adding a proper amount of m-cresol solvent and cooling to obtain a block polyimide solution with the solid content of 18 wt%.
The resulting block polyimide solution was poured into a mixture of methanol and water, washed 3 times, and dried at 150 ℃ for 12 hours. Finally, block polyimide solid is obtained. The block polyimide is designated 6FDA-bisAPAF/DETDA (3000, 0.30).
The resulting solid block polyimide material was mixed with N-methylpyrrolidone to give a block polyimide solution with a preferred solids content of 10 wt%.
Coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the temperature of the glass plate can be controlled by heating, the glass plate is dried for 24 hours at 40 ℃ in a drying oven, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 250 ℃ under vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
Example 2 preparation of a Flat Membrane
Preparation of an oligomeric Block (Block molecular weight 3000, average degree of polymerization 3.87) in a 100mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen purge, 3.66g (10.0 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF) were dissolved in 25g of m-cresol under a nitrogen atmosphere, 6.00g (13.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) were gradually added to the solution, the solution was warmed to 180 ℃ under a nitrogen atmosphere, and stirred for 8 hours.
After the obtained solution was cooled to room temperature, 75g of m-cresol was added thereto, 4.81g (27.0 mmol) of diethyltoluenediamine (DETDA) and 10.44g (23.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride were successively added, and then the solution was heated to 180 ℃ under a nitrogen atmosphere and stirred for 8 hours. Then according to the condition of evaporating the solvent, adding a proper amount of m-cresol solvent and cooling to obtain a block polyimide solution with the solid content of 18 wt%.
The resulting block polyimide solution was poured into a mixture of methanol and water, washed 3 times, and dried at 150 ℃ for 12 hours. Finally, block polyimide solid is obtained. The block polyimide is designated 6FDA-bisAPAF/DETDA (3000, 0.37).
Mixing the obtained solid block polyimide material with N-methyl pyrrolidone to obtain a block polyimide solution with the solid content of 10wt% preferably;
coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the temperature of the glass plate can be controlled by heating, the glass plate is dried for 24 hours at 40 ℃ in a drying oven, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 250 ℃ in a vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
Example 3 preparation of Flat sheet Membrane
Preparation of an oligomeric Block (Block molecular weight 3000, average degree of polymerization 3.87) in a 100mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen purge, 3.66g (10.0 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF) were dissolved in 25g of m-cresol under a nitrogen atmosphere, 6.00g (13.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) were gradually added to the solution, the solution was warmed to 180 ℃ under a nitrogen atmosphere, and stirred for 8 hours.
After the obtained solution was cooled to room temperature, 75g of m-cresol was added thereto, and 3.57g (20.0 mmol) of diethyltoluenediamine (DETDA) and 7.33g (16.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride were sequentially added thereto, and then the solution was heated to 180 ℃ under a nitrogen atmosphere and stirred for 8 hours. Then according to the condition of evaporating the solvent, adding a proper amount of m-cresol solvent and cooling to obtain a block polyimide solution with the solid content of 18 wt%.
The resulting block polyimide solution was poured into a mixture of methanol and water, washed 3 times, and dried at 150 ℃ for 12 hours. Finally, the block polyimide solid is obtained. The block polyimide is designated 6FDA-bisAPAF/DETDA (3000,0.50).
Mixing the obtained solid block polyimide material with N-methyl pyrrolidone to obtain a block polyimide solution with the solid content of 10wt% preferably;
coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the temperature of the glass plate can be controlled by heating, the glass plate is dried for 24 hours at 40 ℃ in a drying oven, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 250 ℃ in a vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
Example 4 preparation of Flat sheet Membrane
Preparation of the oligomeric Block (Block molecular weight 7000, average degree of polymerization 9.04) in a 100mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen flushing, 3.66g (10.0 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisasAPAF) were dissolved in 25g of m-cresol under nitrogen, 6.00g (11.2 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) were added stepwise to the solution, the solution was warmed to 180 ℃ under nitrogen, and stirred for 8 hours.
After the obtained solution was cooled to room temperature, 100g of m-cresol was added thereto, 5.94g (33.3 mmol) of diethyltoluenediamine (DETDA) and 14.26g (32.1 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride were successively added, and then the solution was heated to 180 ℃ under a nitrogen atmosphere and stirred for 8 hours. Then according to the condition of evaporating the solvent, adding a proper amount of m-cresol solvent and cooling to obtain a block polyimide solution with the solid content of 18 wt%.
The resulting block polyimide solution was poured into a mixture of methanol and water, washed 3 times, and dried at 150 ℃ for 12 hours. Finally, block polyimide solid is obtained. The block polyimide is designated 6FDA-bisAPAF/DETDA (7000, 0.30).
Mixing the obtained solid block polyimide material with N-methyl pyrrolidone to obtain a block polyimide solution with the solid content of 10wt% preferably;
coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the glass plate can be dried for 24 hours at 40 ℃ in a drying oven by heating to regulate the temperature, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 250 ℃ in a vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
Example 5 preparation of Flat sheet Membrane
Preparation of the oligomeric Block (Block molecular weight 7000, average degree of polymerization 9.04) in a 100mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen flushing, 3.66g (10.0 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisasAPAF) were dissolved in 25g of m-cresol under nitrogen, 6.00g (11.2 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) were added stepwise to the solution, the solution was warmed to 180 ℃ under nitrogen, and stirred for 8 hours.
After the solution obtained had cooled to room temperature, 100g of m-cresol were added, followed by 4.82g (27.0 mmol) of diethyltoluenediamine (DETDA) and 11.51g (25.9 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride and the solution was then warmed to 180 ℃ under a nitrogen atmosphere and stirred for 8 hours. Then according to the condition of evaporating the solvent, adding a proper amount of m-cresol solvent and cooling to obtain a block polyimide solution with the solid content of 18 wt%.
The resulting block polyimide solution was poured into a mixture of methanol and water, washed 3 times, and dried at 150 ℃ for 12 hours. Finally, the block polyimide solid is obtained. The block polyimide was designated 6FDA-bisAPAF/DETDA (7000, 0.37).
Mixing the obtained solid block polyimide material with N-methyl pyrrolidone to obtain a block polyimide solution with the solid content of 10wt% preferably;
coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the temperature of the glass plate can be controlled by heating, the glass plate is dried for 24 hours at 40 ℃ in a drying oven, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 250 ℃ in a vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
EXAMPLE 6 preparation of Flat sheet Membrane
Preparation of an oligomeric Block (Block molecular weight 3000, average degree of polymerization 3.87) in a 250mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen purge, maintaining the system temperature at 5 deg.C, 3.66g (10.0 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPF) was dissolved in 25g of N-methylpyrrolidone under a nitrogen atmosphere, 6.00g (13.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) was gradually added to the solution, and reacted at 5 deg.C for 1h. Subsequently, the reaction system was warmed to 25 ℃ and stirred under a nitrogen atmosphere for 24 hours.
After the obtained solution was cooled to room temperature, 100g of N-methylpyrrolidone was added thereto, and while maintaining the system temperature at 5 ℃, 5.94g (33.3 mmol) of diethyltoluenediamine (DETDA) and 13.24g (29.8 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride were added in this order under a nitrogen atmosphere and reacted at 5 ℃ for 1 hour. Subsequently, the reaction system was heated to 25 ℃ and stirred for 24 hours under a nitrogen atmosphere to obtain a block polyamic acid solution.
6.85g (86.6 mmol) of pyridine and 4.42g (43.3 mmol) of acetic anhydride are added to the obtained block polyamic acid solution, and the mixture is stirred and reacted for 24 to 48 hours, thus obtaining the block polyimide solution. The block polyimide is noted as 6FDA-bisAPAF/DETDA (3000, 0.30).
Coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the glass plate can be dried for 24 hours at 40 ℃ in a drying oven by heating to regulate the temperature, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 250 ℃ in a vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
Example 7 preparation of Flat sheet Membrane
Preparation of an oligomeric Block (Block molecular weight 3000, average degree of polymerization 3.87) in a 100mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen purge, 3.66g (10.0 mmol) of 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (bisAPAF) was dissolved in 25g of NMP under nitrogen atmosphere at 0 ℃, 6.00g (13.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) was gradually added to the solution, and the reaction was stirred at 0 ℃ for 2h. Then, the reaction system is heated to 25 ℃, stirred and reacted for 24 hours,
the solution obtained was cooled to 0 ℃ and 100g NMP were added, followed by 5.94g (33.3 mmol) diethyltoluenediamine (DETDA) and 13.24g (29.8 mmol) 4,4' - (hexafluoroisopropylene) diphthalic anhydride and stirring at 0 ℃ under nitrogen for 2h and 8 h. Then, the temperature of the reaction system is raised to 25 ℃, the reaction is stirred for 24 hours,
the resulting block polyimide solution was poured into a mixture of methanol and water, washed 3 times, and dried at 150 ℃ for 12 hours. Finally, block polyimide solid is obtained. The block polyimide is noted as 6FDA-bisAPAF/DETDA (3000, 0.30).
Coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the temperature of the glass plate can be controlled by heating, the glass plate is dried for 24 hours at 40 ℃ in a drying oven, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 320 ℃ in a vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
EXAMPLE 8 preparation of Flat sheet Membrane
Preparation of an oligomeric Block (Block molecular weight 3000, average degree of polymerization 4.80) in a 100mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen purge, 2.16g (10.0 mmol) of 3, 3-dihydroxy-4, 4-biphenyldiamine (HAB) were dissolved in 25g of m-cresol under a nitrogen atmosphere, 6.00g (13.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) were gradually added to the solution, the solution was warmed to 180 ℃ under a nitrogen atmosphere, and stirred for 8 hours.
After the obtained solution was cooled to room temperature, 100g of m-cresol was added thereto, 5.94g (33.3 mmol) of diethyltoluenediamine (DETDA) and 13.24g (29.8 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride were successively added, and then the solution was heated to 180 ℃ under a nitrogen atmosphere and stirred for 8 hours. Then according to the condition of evaporating the solvent, adding a proper amount of m-cresol solvent and cooling to obtain a block polyimide solution with the solid content of 18 wt%.
The resulting block polyimide solution was poured into a mixture of methanol and water, washed 3 times, and dried at 150 ℃ for 12 hours. Finally, the block polyimide solid is obtained. The block polyimide is noted as 6FDA-HAB/DAM (3000, 0.30).
Mixing the obtained solid block polyimide material with N-methyl pyrrolidone to obtain a block polyimide solution with the solid content of 10wt% preferably;
coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the temperature of the glass plate can be controlled by heating, the glass plate is dried for 24 hours at 40 ℃ in a drying oven, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 250 ℃ in a vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
Example 9 preparation of Flat sheet Membrane
Preparation of an oligomeric Block (Block molecular weight 3000, average degree of polymerization 3.87) in a 100mL flask equipped with a reflux condenser, mechanical stirrer, nitrogen flush, 2.16g (10.0 mmol) of 3, 3-dihydroxy-4, 4-biphenyldiamine (HAB) were dissolved in 25g of m-cresol under nitrogen, 6.00g (13.5 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride (6 FDA) were added stepwise to the solution, the solution was warmed to 180 ℃ under nitrogen, and stirred for 8 hours.
After the solution obtained was allowed to cool to room temperature, 100g of m-cresol was added, followed by 5.35g (30.0 mmol) of diethyltoluenediamine (DETDA), 0.50g (3.33 mmol) of 3, 5-diaminobenzoic acid (DABA) and 13.24g (29.8 mmol) of 4,4' - (hexafluoroisopropylene) diphthalic anhydride, and the solution was heated to 180 ℃ under a nitrogen atmosphere and stirred for 8 hours. Then according to the condition of distilling the solvent, adding a proper amount of m-cresol solvent and cooling to obtain a block polyimide solution with the solid content of 18 wt%.
The resulting block polyimide solution was poured into a mixture of methanol and water, washed 3 times, and dried at 150 ℃ for 12 hours. Finally, block polyimide solid is obtained. The block polyimide is designated 6FDA-bisAPAF/DETDA & DABA (3000, 0.30).
Mixing the obtained solid block polyimide material with N-methyl pyrrolidone to obtain a block polyimide solution with the solid content of 10wt% preferably;
coating the block polyimide solution on a glass plate by using a scraper with a gap of 500 mu m; the temperature of the glass plate can be controlled by heating, the glass plate is dried for 24 hours at 40 ℃ in a drying oven, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then dried for 1 hour at 250 ℃ in a vacuum/nitrogen atmosphere to obtain the gas separation flat membrane.
EXAMPLE 10 preparation of Flat sheet Membrane
The block polyimide solution obtained in example 6 was coated on a glass plate using a doctor blade having a gap of 500 μm; the temperature of the glass plate can be controlled by heating, the glass plate is dried for 24 hours at 40 ℃ in a drying oven, then the membrane formed after drying is peeled off from the glass plate, dried for 24 hours at 150 ℃, and then treated for 2 hours at 330 ℃ in a nitrogen atmosphere to obtain the gas separation flat membrane.
Examples 11 to 27 preparation of gas separation membranes
Step 1): the flat membranes prepared in examples 1 to 9 were placed in a vacuum oven and purged with an oxidizing atmosphere for half an hour, setting the gas flow rate at 100L/h. Specific gas compositions are shown in table 1 below.
Step 2): keeping the gas flow rate at 100L/h, starting a heating program, setting the temperature rise speed at 5 ℃/min, raising the temperature to a certain temperature, and reacting at the temperature for a certain time. The specific temperatures and holding times are shown in table 1 below.
And step 3): and (4) keeping the gas flow rate, stopping heating after the constant temperature process is finished, and naturally cooling to room temperature to obtain the wine red transparent gas separation membrane.
TABLE 1
Examples 28 to 31 preparation of gas separation membranes
Step 1): the flat membrane for gas separation prepared in example 1 was placed in a vacuum oven and purged with an oxidizing atmosphere for half an hour, with a gas flow rate of 100L/h being set. Specific gas compositions are shown in table 2 below.
Step 2): the gas flow rate is kept at 100L/h, the heating program is started, the temperature rising speed is set to be 5 ℃/min, the temperature is raised to a certain temperature, and the reaction is carried out at the temperature for a certain time, wherein the specific temperature and the constant temperature time are shown in the following table 2.
Step 3): keeping the gas flow rate at 100L/h, cooling to a certain temperature, and reacting at the constant temperature for a certain time. The specific temperatures and holding times are shown in Table 2 below.
Step 4): and (4) keeping the gas flow rate, stopping heating after the constant temperature process is finished, and naturally cooling to room temperature to obtain the wine red transparent gas separation membrane.
TABLE 2
Examples 32 to 33
Step 1): the flat gas separation membrane prepared in example 1 was placed in an oven and purged with nitrogen until the oxygen content in the outlet gas was below 100ppm, setting the gas flow rate at 100L/h.
Step 2): keeping the gas flow rate at 100L/h, starting a heating program, setting the heating speed at 5 ℃/min, heating to a certain temperature, reacting at the constant temperature for a certain time, stopping heating after the constant temperature process is finished, and naturally cooling to room temperature. Specific temperatures and holding times are shown in Table 3 below.
Step 3): and (3) introducing air into the oven, starting a heating program, setting the heating speed to be 5 ℃/min, heating to a certain temperature, and reacting at the constant temperature for a certain time. Specific temperatures and holding times are shown in Table 3 below.
And step 4): and (4) keeping the gas flow rate, stopping heating after the constant temperature process is finished, and naturally cooling to room temperature to obtain the wine red transparent gas separation membrane.
TABLE 3
Test example 1
The membrane samples obtained in the above examples were tested for permeability and selectivity.
The permeability measurement method is as follows:
Barrer(1Barrer＝10 -10 cm 3 (STP)cm/(cm 2 s cmHg)) as a unit of gas permeability. The permeability of the gas is measured by the volumetric transformation method. Applying a gas with a certain pressure on one side of the prepared gas separation membrane. While on the other side, the permeate side, the change in pressure over time was recorded. The gas permeability was calculated by the following formula:
wherein:
P-Permeability in Barrer (10) -10 cm 3 (STP)·cm/(cm 2 ·s·cmHg))；
V-volume of the permeate side in cm 3 ；
l-film thickness in cm;
t-test temperature in K;
Δ p — pressure difference between feed side and permeate side in cmHg;
dp/dt-increase in pressure per unit time on the permeate side, in cmHg. S -1 ；
The selectivity of the different gas pairs is that of pure gas, and the selectivity of the two gases is calculated from the ratio of the permeability of each gas:
α＝P 1 /P 2 ；
wherein: α -ideal gas selectivity;
P 1 permeability of the gas 1;
P 2 permeability of gas 2.
The selectivity calculation formula is α (a/B) = P (a)/P (B), where P (a) and P (B) represent the gas permeability coefficients of gases a and B, respectively.
Tables 4 and 5 show the gas permeability coefficients and partial gas selectivities of examples 11 to 33.
TABLE 4
TABLE 5
In the thermal oxidation treatment process, oxidative crosslinking and thermal cracking occur simultaneously, and the thermal oxidation degree can be regulated and controlled by adjusting factors such as the heat treatment atmosphere (examples 12 and 13), the content of the block containing ortho-hydroxyl (examples 12 and 10), the length of the block containing ortho-hydroxyl (examples 11 and 21), the heat treatment time (examples 12 and 15) and the like, so that the gas separation performance of the thermal oxidation block gas separation membrane can be adjusted, the requirements of practical application are met, and the gas separation membrane with excellent performance is obtained.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A block copolymer is characterized in that the structural formula of the block copolymer is shown as a formula I:
the block copolymer comprises a block A represented by formula II and a block B represented by formula III;
wherein the average polymerization degree m of the block A is 1-100;
the average polymerization degree n of the block B is 1-100;
R 1 is selected from R 1a 、R 1b 、R 1c 、R 1d 、R 1e 、R 1f 、R 1g One of (a) and (b);
R 2 is selected from R 2a 、R 2b 、R 2c 、R 2d 、R 2e 、R 2f One of (a) and (b);
R 3 is selected from R 3a Or R 3b One of the two kinds of the components;
wherein L is 1 ，L 2 ，L 3 ，L 4 Independently selected from-H, -F, -Cl, -Br, -I, -CF 3 ，-CCl 3 ，-CBr 3 ，-CI 3 ，-CH 3 ，-C 2 H 5 ，-NO 2 -CN, -COOH.
2. The block copolymer according to claim 1,
said R is 3 Middle L 1 ，L 2 ，L 3 ，L 4 In which at most two are-CH 3 ；
The block A is obtained by polymerizing dianhydride a and diamine b;
the block B is obtained by polymerizing dianhydride a and diamine c;
the structure of dianhydride a is shown as a; the structure of the diamine b is shown as b; the structure of the diamine c is shown as c;
3. the method for producing a block copolymer according to any one of claims 1 or 2, wherein the production method is selected from the group consisting of method X or method Y;
wherein, the method X comprises:
(X1) mixing a raw material containing diamine and excessive dianhydride with a solvent I, stirring and reacting at 100-250 ℃ for 2-24 h, stopping heating and cooling to room temperature to obtain a solution a1;
(X2) mixing dianhydride and excessive diamine with the solution a1, reacting for 2-24 h at 100-250 ℃, adding a solvent, washing, and treating for 2-24 h at 100-250 ℃ to obtain the block polyimide material;
the method (Y) comprises:
(Y1) mixing a raw material containing diamine and excessive dianhydride with a solvent I at 0-5 ℃, stirring for 1-2 h, heating to 20-30 ℃, and stirring for 24-48h to obtain a solution b1;
(Y2) mixing dianhydride and excessive diamine with the solution b1 at the temperature of 0-5 ℃, stirring for 1-2 h, heating to 20-30 ℃, and stirring for 24-48h to obtain a block polyamic acid solution;
(Y3) adding a tertiary amine catalyst and acetic anhydride after the stirring in the step (Y2); stirring and reacting for 24-48h, pouring alcohol lotion, washing and drying, and processing for 2-24 h at 100-250 ℃ to obtain the block polyimide material.
4. The production method according to claim 3, characterized in that:
in the step (X1) or the step (Y1), the molar ratio of the dianhydride to the diamine is 1-2;
preferably, the molar ratio of dianhydride to diamine is 1.1 to 1.9;
the solvent I is at least one selected from N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or m-cresol;
the diamine selected in the step (X1) and the diamine selected in the step (X2) are not diamine b at the same time, and are not diamine c at the same time;
the diamine selected in the step (Y1) is not the diamine b at the same time as the diamine selected in the step (Y2), and is not the diamine c at the same time;
in the method X or the method Y, the molar ratio of the diamine b to the diamine c is 0.01 to 100;
preferably, the molar ratio of diamine b to diamine c is from 0.1 to 10;
wherein the molar ratio of the total amount of diamine b and diamine c to the total amount of dianhydride in method X or Y is 0.8;
preferably, the molar ratio of the total amount of diamine b and diamine c to the total amount of dianhydride used in process X or Y is from 0.95 to 1.05;
in the step (X2) or the step (Y2), the washing is performed with a reagent selected from at least one of methanol, ethanol, and water;
in the step (Y3), the tertiary amine catalyst is at least one selected from pyridine and triethylene diamine;
the molar ratio of the tertiary amine catalyst to the total amount of acetic anhydride to dianhydride is 2:1:1.
5. a flat sheet membrane, wherein a raw material of the flat sheet membrane contains the block polyimide material according to claim 1 or 2 or the block polyimide material or the block polyamic acid solution prepared by the preparation method according to claim 3 or 4.
6. A method for preparing a flat sheet membrane, comprising the steps of:
preparing a flat membrane from the block polyimide material or the block polyamic acid solution by a membrane scraping method;
preferably, the first and second liquid crystal display panels are,
the doctor blade method is selected from method (E) or method (F);
the method (E) comprises:
(E1) Coating the casting solution containing the block polyimide material on the surface of a substrate, drying, and stripping the obtained film from the substrate;
the substrate is selected from a glass plate or a polytetrafluoroethylene plate;
(E2) Continuously drying under vacuum or nitrogen atmosphere;
(E3) Heating to more than 200 ℃, and continuously drying in vacuum or nitrogen atmosphere;
wherein the drying temperature in the step (E1) is 40-100 ℃, and the drying time is 24-48 hours;
(E2) The drying temperature is 100-200 ℃, and the drying time is 12-24 hours;
preferably, the drying temperature in (E2) is 100 to 150 ℃;
preferably, the drying temperature in (E2) is 130 to 160 ℃;
e3 The drying temperature in the step (a) is 200-250 ℃ and the time is 1-4 hours;
the casting solution also contains a solvent II;
the solvent II is at least one selected from N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone or m-cresol;
the mass percentage concentration of the block polyimide material in the casting solution is 5-15 wt%;
the method (F) comprises:
(F1) Directly coating the block polyamic acid solution obtained in the step (Y2) in the method (Y) on the surface of a substrate, drying, and peeling the obtained film from the substrate;
the substrate is selected from a glass plate or a polytetrafluoroethylene plate;
(F2) Continuously drying under vacuum or nitrogen atmosphere;
(F3) Further heat treatment under nitrogen atmosphere;
wherein the drying temperature in the step (F1) is 40-100 ℃, and the drying time is 24-48 hours;
(F2) The drying temperature is 100-200 ℃, and the time is 12-24 hours;
(F3) The heat treatment temperature is 250-350 ℃, and the time is 1-12 hours;
preferably, the drying temperature in (F2) is 100 to 150 ℃;
preferably, the drying temperature in (F2) is 130 to 160 ℃.
7. A gas separation membrane obtained by heating the flat sheet membrane according to claim 5 or the flat sheet membrane produced by the method according to claim 6 in an oxidizing atmosphere.
8. A method for producing a gas separation membrane, characterized by comprising the method (G), the method (H), and the method (J);
wherein method (G) comprises the steps of: heating the flat sheet membrane prepared by the preparation method of claim 6 in an oxidizing atmosphere to obtain the gas separation membrane;
the oxidizing atmosphere is a mixed atmosphere containing oxygen and inert gas;
the inactive gas is at least one of nitrogen, helium, argon, krypton, xenon or carbon dioxide;
the volume content of the oxygen is 0.1-50%;
the temperature of the treatment under the oxidizing atmosphere is 220-450 ℃, and the time is 1-5 hours;
preferably, the temperature of the treatment under the oxidizing atmosphere is 300-440 ℃;
preferably, the temperature of the treatment under the oxidizing atmosphere is 350-440 ℃;
the method (H) comprises the following steps:
(H1) Heating the flat membrane prepared by the preparation method of claim 6 in an oxidizing atmosphere, and keeping the temperature for a certain time;
(H2) Reducing the temperature to a specific temperature at a certain speed under the same atmosphere, and keeping the temperature for a certain time to obtain the gas separation membrane;
the volume content of the oxygen is 0.1-50%;
the cooling rate is 0.1-10 ℃/min;
preferably, the constant temperature of the first stage is 420-440 ℃, and the constant temperature time is 1-2 hours;
preferably, the constant temperature of the second stage is 360-400 ℃, and the constant temperature time is 2-4 hours;
the method (J) comprises the steps of:
(J1) Heating the flat membrane prepared by the preparation method of claim 6 in an inert atmosphere, and keeping the temperature for a certain time;
(J2) Heating in an oxidizing atmosphere and keeping the temperature constant for a certain time to obtain the gas separation membrane;
in the inert atmosphere, at least one of nitrogen or argon is selected, and the oxygen content is less than 100ppm;
in the oxidizing atmosphere, the volume content of oxygen is 0.1-50%;
preferably, the constant temperature of the first stage is 400-440 ℃, and the constant temperature time is 1-4 hours;
preferably, the constant temperature of the second stage is 380-450 ℃, and the constant temperature time is 2-6 hours.
9. Use of the gas separation membrane of claim 7 or the gas separation membrane produced by the method of claim 8 in the separation of a gas mixture,
the mixed gas is selected from H 2 And CH 4 Mixed gas of He and CH 4 Mixed gas of CO 2 And CH 4 Mixed gas of O 2 And N 2 Mixed gas of H 2 And N 2 Mixed gas of CO 2 And N 2 Mixed gas of H 2 And CO 2 At least one of the mixed gas.
10. Use according to claim 9,
the mixed gas is H 2 And CH 4 H of the polymer film in mixed gas 2 The selectivity of (A) is 10 to 300;
the mixed gas is He and CH 4 When mixed gas is adopted, the selectivity of He of the polymer film is 8-300;
the mixed gas is CO 2 And CH 4 When mixed with gas, the polymer filmCO of (2) 2 The selectivity of (A) is 10 to 120.
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