CN115253728A - Preparation method of polyimide fiber solvent-resistant nanofiltration membrane - Google Patents
Preparation method of polyimide fiber solvent-resistant nanofiltration membrane Download PDFInfo
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- CN115253728A CN115253728A CN202211026244.8A CN202211026244A CN115253728A CN 115253728 A CN115253728 A CN 115253728A CN 202211026244 A CN202211026244 A CN 202211026244A CN 115253728 A CN115253728 A CN 115253728A
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- 239000012528 membrane Substances 0.000 title claims abstract description 79
- 239000000835 fiber Substances 0.000 title claims abstract description 50
- 238000003849 solvent resist ant nanofiltration Methods 0.000 title claims abstract description 43
- 239000004642 Polyimide Substances 0.000 title claims abstract description 41
- 229920001721 polyimide Polymers 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 51
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 32
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 23
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 238000004132 cross linking Methods 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 11
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 11
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 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 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 10
- 230000004907 flux Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 6
- 230000007774 longterm Effects 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 238000000926 separation method Methods 0.000 description 15
- 229940081623 rose bengal Drugs 0.000 description 11
- IICCLYANAQEHCI-UHFFFAOYSA-N 4,5,6,7-tetrachloro-3',6'-dihydroxy-2',4',5',7'-tetraiodospiro[2-benzofuran-3,9'-xanthene]-1-one Chemical compound O1C(=O)C(C(=C(Cl)C(Cl)=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 IICCLYANAQEHCI-UHFFFAOYSA-N 0.000 description 8
- 229930187593 rose bengal Natural products 0.000 description 8
- STRXNPAVPKGJQR-UHFFFAOYSA-N rose bengal A Natural products O1C(=O)C(C(=CC=C2Cl)Cl)=C2C21C1=CC(I)=C(O)C(I)=C1OC1=C(I)C(O)=C(I)C=C21 STRXNPAVPKGJQR-UHFFFAOYSA-N 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 6
- 238000009987 spinning Methods 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000010998 test method Methods 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004935 solvent resistant nanofiltration (SRNF) membrane Substances 0.000 description 1
- 239000010887 waste solvent Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a polyimide fiber solvent-resistant nanofiltration membrane, which comprises the following steps: (1) obtaining a polyamic acid solution; (2) Mixing the polyamic acid solution with the polymer aqueous solution, and performing electrostatic spinning to obtain a fiber membrane; the polymer is polyvinyl alcohol and/or polyethylene glycol; (3) Carrying out heat treatment on the fiber membrane obtained in the step (2) for primary imidization; (4) Immersing the membrane obtained in the step (3) into a mixed solution of pyridine and acetic anhydride for secondary imidization; (5) And (4) immersing the membrane obtained in the step (3) into an amine solution for a crosslinking reaction to obtain the polyimide fiber solvent-resistant nanofiltration membrane. The invention adopts the electrostatic spinning method to prepare the polyimide fiber solvent-resistant nanofiltration membrane, and has the advantages of large solvent permeation flux, good chemical stability and long-term service performance.
Description
Technical Field
The invention belongs to the field of membrane materials and separation application thereof, and particularly relates to a preparation method of a polyimide fiber solvent-resistant nanofiltration membrane.
Background
A large amount of organic solvents are needed in the fields of chemical industry, food, medicine and the like, and efficient separation of substances in the organic solvents and treatment of waste solvents are important problems in practical production. Compared with the traditional separation modes such as distillation, extraction, crystallization and the like, the membrane technology has the advantages of low energy consumption, low cost, easy industrial amplification and the like. The solvent-resistant nanofiltration membrane belongs to a special nanofiltration membrane, has the aperture of about 1nm, and can separate molecules with the molecular weight of 200-1000g/mol from an organic solvent. At present, the solvent-resistant nanofiltration membrane mainly has two structural forms, namely an asymmetric membrane and a composite membrane, and compared with the asymmetric membrane, the asymmetric membrane has excellent chemical stability, and the commercial solvent-resistant nanofiltration membrane mainly takes the asymmetric membrane as a main component. Polyimide is widely used for preparing asymmetric solvent-resistant nanofiltration membranes as a polymer with excellent performance, but the permeation flux is low (Journal of Membrane Science,2002,205 (1-2): 191-202.). Although the permeation flux of the polyimide solvent-resistant nanofiltration membrane can be improved by adding nanomaterials such as graphene oxide (Chemical Engineering Research and Design,2019,146, 182-189.), carbon nanotubes (Chemical Engineering Journal,2018,345, 174-185) and MOF (Environmental Research,2020, 183.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method of a polyimide fiber solvent-resistant nanofiltration membrane.
The specific technical scheme is as follows:
a preparation method of a polyimide fiber solvent-resistant nanofiltration membrane comprises the following steps:
(1) Obtaining polyamic acid, specifically a polyamic acid solution with a certain solid content;
(2) Mixing the polyamic acid solution with the polymer aqueous solution, and performing electrostatic spinning to obtain a fiber membrane; the polymer is polyvinyl alcohol and/or polyethylene glycol;
(3) Carrying out heat treatment on the fiber membrane obtained in the step (2) for primary imidization;
(4) Immersing the membrane obtained in the step (3) into a mixed solution of pyridine and acetic anhydride for secondary imidization;
(5) And (5) immersing the membrane obtained in the step (4) into an amine solution for cross-linking reaction to obtain the polyimide fiber solvent-resistant nanofiltration membrane.
Further, in the step (1): the polyamic acid solution is prepared by synthesizing 3,3', 4' -biphenyl tetracarboxylic dianhydride and m-phenylenediamine with the molar ratio of (0.8-1.2) to 1. The molar ratio of 3,3',4,4' -biphenyltetracarboxylic dianhydride to m-phenylenediamine is preferably 1.2.
Further, in the step (1): the solid content of the polyamic acid solution is 20-40%.
Further, in the step (1): the solvent for the reaction is N, N-dimethylacetamide.
Further, in the step (1): reaction in N 2 Under the protection of the catalyst.
Further, in the step (1): the reaction temperature is preferably 15 to 50 ℃.
Further, in the step (1): the reaction time is preferably 0.5 to 2 hours.
Further, in the step (2): the concentration of the polymer aqueous solution is 5-35 wt%.
Further, in the step (2): the mass ratio of the polyamic acid solution to the polymer aqueous solution is (0.1-10): 1.
Further, in the step (2): the electrostatic spinning takes non-woven fabrics as a substrate.
Further, in the step (2): the conditions for electrospinning are preferably: the voltage is 10-25 kV, and the spinning speed is 0.5-5 mL/h.
Further, in the step (3): the heat treatment temperature is 50-200 ℃, and the heat treatment time is 5-20 hours. The heat treatment is preferably carried out in an oven.
Further, in the step (4): in the mixed solution of pyridine and acetic anhydride, the molar ratio of pyridine to acetic anhydride is (0.5-3): 1.
Further, in the step (4): the soaking time is 2-30 hours.
Further, in the step (5): the amine is one or a mixture of more than two of ethylenediamine, polyethyleneimine, piperazine, m-phenylenediamine and hexamethylenediamine.
Further, in the step (5): the amine solution is an aqueous solution of amine, and the concentration of the amine solution is 0.2 to 10 weight percent.
Further, in the step (5): the crosslinking time is 1 to 30 hours.
The invention has the following beneficial effects:
the invention adopts the electrostatic spinning method to prepare the polyimide fiber solvent-resistant nanofiltration membrane, and has the advantages of large solvent permeation flux, good chemical stability and long-term service performance.
Drawings
FIG. 1 shows the separation performance of the polyimide fiber solvent-resistant nanofiltration membrane in example 1 of the present invention on three solvent systems;
FIG. 2 is a graph showing the long-term service performance change of the polyimide fiber solvent-resistant nanofiltration membrane in the ethanol-rose bengal system in example 1 of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are included to illustrate the invention and not to limit the scope of the invention.
Example 1
The preparation method of the polyimide fiber solvent-resistant nanofiltration membrane comprises the following steps:
(1) At N 2 Under protection, 3', 4' -biphenyl tetracarboxylic dianhydride and m-phenylenediamine in a molar ratio of 1.2 are put into reaction, N-dimethylacetamide is used as a solvent, and the reaction is carried out for 2 hours at 15 ℃ to synthesize a polyamic acid solution with 20% of solid content;
(2) Mixing the polyamic acid solution obtained in the step (1) with a 5wt% polyvinyl alcohol aqueous solution according to a mass ratio of 0.1; electrostatic spinning conditions: the voltage is 25kV, and the spinning speed is 5mL/h;
(3) Placing the fiber membrane obtained in the step (2) in an oven at 50 ℃ for 20 hours, and carrying out primary imidization;
(4) Immersing the membrane obtained in the step (3) into a mixed solution of pyridine and acetic anhydride at the normal temperature, wherein the molar ratio of the pyridine to the acetic anhydride is 1.6;
(5) And (3) immersing the membrane obtained in the step (4) into a 0.2wt% ethylenediamine aqueous solution for crosslinking reaction for 30 hours at normal temperature to obtain the polyimide fiber solvent-resistant nanofiltration membrane.
The polyimide fiber solvent-resistant nanofiltration membrane obtained by the method is subjected to separation performance test, and the test method comprises the following steps: the test is carried out under the condition of cross flow, the test pressure is 0.5MPa, the feed liquid is 0.5g/L rose bengal ethanol solution, 0.5g/L rose bengal methanol solution and 0.5g/L rose bengal isopropanol solution, and the temperature of the feed liquid is 25 ℃.
The separation performance of the polyimide fiber solvent-resistant nanofiltration membrane on an ethanol-rose bengal system is measured as follows: the ethanol permeation flux is 12.1 L.m -2 ·h -1 ·bar -1 The retention of rose bengal is 96.9%.
The separation performance of the polyimide fiber solvent-resistant nanofiltration membrane on different solvent systems is shown in fig. 1, and the obtained polyimide fiber solvent-resistant nanofiltration membrane has high interception capability in methanol, ethanol and isopropanol, which indicates that the polyimide fiber solvent-resistant nanofiltration membrane has good chemical stability.
The measured change of the long-term service performance of the polyimide fiber solvent-resistant nanofiltration membrane on an ethanol-rose bengal system is shown in fig. 2, and the obtained polyimide fiber solvent-resistant nanofiltration membrane has good long-term stability.
Example 2
The preparation method of the polyimide fiber solvent-resistant nanofiltration membrane comprises the following steps:
(1) At N 2 Under protection, 3', 4' -biphenyl tetracarboxylic dianhydride and m-phenylenediamine in a molar ratio of 1.2 are put into reaction, N-dimethylacetamide is used as a solvent, and the reaction is carried out for 0.5 hour at 50 ℃ to synthesize a polyamic acid solution with the solid content of 40%;
(2) Mixing the polyamic acid solution obtained in the step (1) with a polyvinyl alcohol aqueous solution with the mass ratio of 10; electrostatic spinning conditions: the voltage is 10kV, and the spinning speed is 0.5mL/h;
(3) Placing the fiber membrane obtained in the step (2) in an oven at 200 ℃ for 5 hours for primary imidization;
(4) Immersing the membrane obtained in the step (3) into a mixed solution of pyridine and acetic anhydride at the normal temperature, wherein the molar ratio of the pyridine to the acetic anhydride is 2.5;
(5) And (5) immersing the membrane obtained in the step (4) into a 10wt% m-phenylenediamine aqueous solution at normal temperature for crosslinking reaction for 30 hours to obtain the polyimide fiber solvent-resistant nanofiltration membrane.
The polyimide fiber obtained above was subjected to a separation performance test using a solvent-resistant nanofiltration membrane, according to the test method described in example 1. The separation performance of the polyimide fiber solvent-resistant nanofiltration membrane is measured as follows: the ethanol permeation flux is 10.6 L.m -2 ·h -1 ·bar -1 The retention of rose bengal is 98.4%.
Example 3
The preparation method of the polyimide fiber solvent-resistant nanofiltration membrane comprises the following steps:
(1) In N 2 Under protection, 3', 4' -biphenyl tetracarboxylic dianhydride and m-phenylenediamine in a molar ratio of 1.2 are put into reaction, N-dimethylacetamide is used as a solvent, and the reaction is carried out for 1 hour at 25 ℃ to synthesize a polyamic acid solution with 20% of solid content;
(2) Mixing the polyamic acid solution obtained in the step (1) with a 20wt% polyethylene glycol aqueous solution according to a mass ratio of 5; electrostatic spinning conditions: the voltage is 20kV, and the spinning speed is 3mL/h;
(3) Placing the fiber membrane obtained in the step (2) in a drying oven at 100 ℃ for 10 hours for primary imidization;
(4) Immersing the membrane obtained in the step (3) into a mixed solution of pyridine and acetic anhydride at the normal temperature, wherein the molar ratio of the pyridine to the acetic anhydride is 0.5;
(5) And (3) immersing the membrane obtained in the step (4) into a 6wt% polyethylene imine water solution for crosslinking reaction for 15 hours at normal temperature to obtain the polyimide fiber solvent-resistant nanofiltration membrane.
The polyimide fiber solvent-resistant nanofiltration membrane obtained above was subjected to a separation performance test, the test method referring to example 1. The separation performance of the polyimide fiber solvent-resistant nanofiltration membrane is measured as follows: ethanol infiltrationThe flux was 9.6 L.m -2 ·h -1 ·bar -1 The retention of rose bengal is 98.8%.
Example 4
The preparation method of the polyimide fiber solvent-resistant nanofiltration membrane comprises the following steps:
(1) In N 2 Under protection, 3', 4' -biphenyl tetracarboxylic dianhydride and m-phenylenediamine in a molar ratio of 1.2 are put into reaction, N-dimethylacetamide is used as a solvent, and the reaction is carried out for 1 hour at 25 ℃ to synthesize a polyamic acid solution with a solid content of 30%;
(2) Mixing the polyamic acid solution obtained in the step (1) with a 20wt% polyethylene glycol aqueous solution according to a mass ratio of 6; electrostatic spinning conditions: the voltage is 25kV, and the spinning speed is 5mL/h;
(3) Placing the fiber membrane obtained in the step (2) in an oven at 100 ℃ for 5 hours for primary imidization;
(4) Immersing the membrane obtained in the step (3) into a mixed solution of pyridine and acetic anhydride at the normal temperature, wherein the molar ratio of the pyridine to the acetic anhydride is 3;
(5) And (3) immersing the membrane obtained in the step (4) into a mixed aqueous solution of 5wt% of polyethyleneimine and piperazine for crosslinking reaction at normal temperature, wherein the mass ratio of the polyethyleneimine to the piperazine is 2.
The polyimide fiber solvent-resistant nanofiltration membrane obtained above was subjected to a separation performance test, the test method referring to example 1. The separation performance of the polyimide fiber solvent-resistant nanofiltration membrane is measured as follows: the ethanol permeation flux is 12.3 L.m -2 ·h -1 ·bar -1 The retention of rose bengal is 98.0%.
Example 5
The preparation method of the polyimide fiber solvent-resistant nanofiltration membrane comprises the following steps:
(1) In N 2 Under protection, 3', 4' -biphenyl tetracarboxylic dianhydride and m-phenylenediamine in a molar ratio of 1.2 are put into reaction, N-dimethylacetamide is used as a solvent, and the reaction is carried out at 30 ℃ for 1Synthesizing a polyamic acid solution with the solid content of 40 percent in hours;
(2) Mixing the polyamic acid solution obtained in the step (1) with 20wt% of mixed aqueous solution of polyethylene glycol and polyvinyl alcohol according to the mass ratio of 1; electrostatic spinning conditions are as follows: the voltage is 10kV, and the spinning speed is 1mL/h;
(3) Placing the fiber membrane obtained in the step (2) in an oven at 150 ℃ for 8 hours for primary imidization;
(4) Immersing the membrane obtained in the step (3) into a mixed solution of pyridine and acetic anhydride at the normal temperature, wherein the molar ratio of the pyridine to the acetic anhydride is 1;
(5) And (3) immersing the membrane obtained in the step (4) into a 1wt% hexamethylene diamine aqueous solution for crosslinking reaction for 10 hours at normal temperature to obtain the polyimide fiber solvent-resistant nanofiltration membrane.
The polyimide fiber solvent-resistant nanofiltration membrane obtained above was subjected to a separation performance test, the test method referring to example 1. The separation performance of the polyimide fiber solvent-resistant nanofiltration membrane is measured as follows: the ethanol permeation flux is 10.7 L.m -2 ·h -1 ·bar -1 The retention of rose bengal is 99.1%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (9)
1. A preparation method of a polyimide fiber solvent-resistant nanofiltration membrane is characterized by comprising the following steps:
(1) Obtaining a polyamic acid solution;
(2) Mixing the polyamic acid solution with the polymer aqueous solution, and performing electrostatic spinning to obtain a fiber membrane; the polymer is polyvinyl alcohol and/or polyethylene glycol;
(3) Carrying out heat treatment on the fiber membrane obtained in the step (2) to carry out primary imidization;
(4) Immersing the membrane obtained in the step (3) into a mixed solution of pyridine and acetic anhydride for secondary imidization;
(5) And (5) immersing the membrane obtained in the step (4) into an amine solution for cross-linking reaction to obtain the polyimide fiber solvent-resistant nanofiltration membrane.
2. The method according to claim 1, wherein in the step (1): the polyamic acid solution is prepared by synthesizing 3,3', 4' -biphenyl tetracarboxylic dianhydride and m-phenylenediamine in a molar ratio of (0.8-1.2): 1.
3. The production method according to claim 1 or 2, characterized in that, in step (1): the solid content of the polyamic acid solution is 20-40%.
4. The production method according to claim 1 or 2, characterized in that in step (2):
the concentration of the polymer aqueous solution is 5-35 wt%;
the mass ratio of the polyamic acid solution to the polymer aqueous solution is (0.1-10): 1.
5. The production method according to claim 1 or 2, characterized in that in step (2): the electrostatic spinning takes non-woven fabrics as a substrate.
6. The production method according to claim 1 or 2, characterized in that, in step (3): the heat treatment temperature is 50-200 ℃, and the heat treatment time is 5-20 hours.
7. The production method according to claim 1 or 2, characterized in that, in step (4):
in the mixed solution of pyridine and acetic anhydride, the molar ratio of pyridine to acetic anhydride is (0.5-3) to 1;
the soaking time is 2-30 hours.
8. The production method according to claim 1 or 2, characterized in that, in step (5):
the amine is one or a mixture of more than two of ethylenediamine, polyethyleneimine, piperazine, m-phenylenediamine and hexamethylenediamine;
the concentration of the amine solution is 0.2-10 wt%;
the crosslinking time is 1 to 30 hours.
9. A polyimide fiber solvent-resistant nanofiltration membrane obtained by applying the preparation method of any one of claims 1 to 8.
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CN105944579A (en) * | 2016-05-26 | 2016-09-21 | 中国海洋大学 | Preparation method of cross-linking modified polyimide organic-solvent-resistant composite membrane and prepared composite membrane as well as application of membrane |
CN107034542A (en) * | 2017-04-20 | 2017-08-11 | 北京化工大学 | A kind of method that three-step approach mixing imidization prepares polyimide fiber |
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