CN113019136B - Polar aprotic organic solvent resistant polyimide separation membrane, preparation and application - Google Patents
Polar aprotic organic solvent resistant polyimide separation membrane, preparation and application Download PDFInfo
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- 239000003960 organic solvent Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 210000004379 membrane Anatomy 0.000 claims abstract description 80
- 239000002121 nanofiber Substances 0.000 claims abstract description 58
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- 210000002469 basement membrane Anatomy 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 20
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 17
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- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 10
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000006068 polycondensation reaction Methods 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000004985 diamines Chemical class 0.000 claims abstract description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 8
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- 238000002791 soaking Methods 0.000 claims description 8
- 239000002344 surface layer Substances 0.000 claims description 8
- 239000010410 layer Substances 0.000 claims description 6
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- RLYCRLGLCUXUPO-UHFFFAOYSA-N 2,6-diaminotoluene Chemical compound CC1=C(N)C=CC=C1N RLYCRLGLCUXUPO-UHFFFAOYSA-N 0.000 claims description 4
- ZVDSMYGTJDFNHN-UHFFFAOYSA-N 2,4,6-trimethylbenzene-1,3-diamine Chemical compound CC1=CC(C)=C(N)C(C)=C1N ZVDSMYGTJDFNHN-UHFFFAOYSA-N 0.000 claims description 2
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 claims description 2
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Natural products C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- UNUDTFPPTQWKMU-UHFFFAOYSA-N 6-(1,1,1,3,3,3-hexafluoropropan-2-ylidene)-N-phenylcyclohexa-2,4-dien-1-amine Chemical compound FC(C(C(F)(F)F)=C1C(C=CC=C1)NC1=CC=CC=C1)(F)F UNUDTFPPTQWKMU-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 229910052757 nitrogen Inorganic materials 0.000 description 14
- 230000004907 flux Effects 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
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- 238000003756 stirring Methods 0.000 description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
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- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 1
- PMTMAFAPLCGXGK-UHFFFAOYSA-N OPDA Natural products CCC=CCC1C(CCCCCCCC(O)=O)C=CC1=O PMTMAFAPLCGXGK-UHFFFAOYSA-N 0.000 description 1
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- 238000001728 nano-filtration Methods 0.000 description 1
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- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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Images
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- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention belongs to the technical field of membrane separation, and particularly relates to a polar aprotic organic solvent resistant polyimide separation membrane, and preparation and application thereof. The preparation method comprises the following steps: (1) adding a diamine monomer into a solvent for dissolving, and then adding a dianhydride monomer for a polycondensation reaction to obtain a polyamic acid solution; (2) preparing polyamic acid nano-fiber by electrostatic spinning of polyamic acid solution; (3) imidizing the polyamide acid nanofiber to prepare a polyimide nanofiber basement membrane; (4) and preparing a polyamide selection layer on the surface of the polyimide nanofiber basement membrane by an interfacial polymerization method to obtain the polyimide separation membrane. The polyimide separation membrane is prepared by adopting a simple method of combining polyamide acid synthesis with electrostatic spinning, thermal imidization and interfacial polymerization, and has excellent polar aprotic organic solvent resistance and excellent separation selectivity.
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to a polar aprotic organic solvent resistant polyimide separation membrane, and preparation and application thereof.
Background
Polar aprotic organic solvents such as N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC), N-methylpyrrolidone (NMP) and Dimethylsulfoxide (DMSO) are important and commonly used solvents in the chemical and pharmaceutical industries and are widely used in organic synthesis, spinning of polymer fibers, reaction media for producing active pharmaceutical ingredients, and the like. However, the high cost of organic solvent recovery and the ever-increasing environmental demands for large solvent emissions continue to be major problems facing the chemical and pharmaceutical industries.
The membrane separation process has the advantages of greenness, high efficiency, simple operation, low equipment investment cost, small occupied area, no phase change and the like, and has wide application prospect in the fields of organic solvent recovery, organic solvent system separation and the like. For the membrane separation process, a separation membrane with excellent and stable performance is a key to successful application of the membrane process, and particularly for the membrane separation process of the above-mentioned organic solvent treatment, it is necessary to ensure that the membrane is not damaged by the organic solvent during the separation process and a stable separation effect is maintained.
At present, membranes used for separation and extraction of the organic solvent at home and abroad are mainly divided into two types; inorganic solvent-resistant films and solvent-resistant polymer films. Common polymer membranes that can be used as solvent resistance include Polyetheretherketone (PEEK), Polyacrylonitrile (PAN), Polybenzimidazole (PBI), Polyamideimide (PAI), Polyetherimide (PEI), Polyimide (PI), and the like. However, most polymer membranes are easy to swell in organic solvents, especially in polar aprotic organic solvents, unmodified polymer membranes can be completely dissolved, and high-performance polymer membranes resistant to polar aprotic organic solvents are important problems to be solved in the field of separation membranes.
Polyimide is an excellent solvent-resistant polymer film material because of its high solvent resistance, excellent mechanical strength and good heat resistance. The solvent-resistant polymer membrane which is most widely applied at present is mainly a polyimide membrane prepared by a phase inversion method, and then the polyimide membrane is modified by chemical crosslinking, so that the polyimide membrane has good polar aprotic organic solvent resistance. However, the membranes prepared by the method generally have the disadvantages of low flux, long modification time, high toxicity of the used chemical crosslinking agent and the like. Therefore, the method for preparing the polyimide film with high flux and strong polar organic solvent resistance, which is simple to operate and environment-friendly, is researched, and has very important research and industrial application significance.
CN106099013B discloses a preparation method of a polyimide porous diaphragm, and particularly discloses that PVDF and PAA are co-dissolved in DMF to prepare spinning solution; then the spinning solution is sprayed out by an electrostatic spinning machine to obtain electrostatic spinning with the diameter of nanometer level, and then the electrostatic spinning with nanometer level is used for preparing a blended fiber membrane; and drying the blended fiber membrane, performing gradient heat treatment at 140 ℃ and 260 ℃, and cooling to obtain the polyimide porous membrane. The polyimide porous membrane prepared by the technical scheme has good thermal stability, high strength, high liquid absorption rate and low implementation cost, but cannot be applied to separation and filtration and solvent recovery of a polar aprotic organic solvent system.
In view of the above, the prior art still lacks a high performance polyimide separation membrane resistant to polar aprotic organic solvents.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a polyimide separation membrane resistant to a polar aprotic organic solvent, and aims to prepare a polyimide membrane with high flux and resistance to the polar aprotic organic solvent through autonomous synthesis of a polyimide precursor and combination of electrostatic spinning and heat treatment modification, prepare a thin film composite membrane (TFC) membrane with excellent performance, and apply the prepared TFC membrane based on the polyimide to separation application of a polar aprotic organic solvent system, so that the problems of poor separation performance and the like of the existing polyimide membrane are solved. The detailed technical scheme of the invention is as follows.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a polyimide separation membrane resistant to a polar aprotic organic solvent, comprising the steps of:
(1) adding a diamine monomer into a solvent for dissolving, and then adding a dianhydride monomer for a polycondensation reaction to obtain a polyamic acid solution;
(2) preparing polyamic acid nano-fiber by electrostatic spinning of polyamic acid solution;
(3) imidizing the polyamide acid nanofiber to obtain a polyimide nanofiber basement membrane;
(4) and preparing a polyamide selection layer on the surface of the polyimide nanofiber basement membrane by an interfacial polymerization method to obtain the polyimide separation membrane.
Preferably, the imidization is thermal imidization, the thermal imidization temperature is 150-400 ℃, the time of the thermal imidization is 0.5-10h, and the thermal imidization is one of nitrogen atmosphere thermal imidization, argon atmosphere thermal imidization and vacuum thermal imidization.
Preferably, the electrostatic spinning voltage is 10-30kV, the temperature is 10-60 ℃, and the relative humidity is 20-60%.
Preferably, the diamine monomer is one or more of 2, 6-diaminotoluene (2,6-DAT), 4 ' -diaminodiphenyl ether (ODA), 4 ' -diaminodiphenylmethane (MDA), 2,4, 6-trimethyl-1, 3-phenylenediamine (DAM), 4 ' - (hexafluoroisopropylidene) diphenylamine (6FpDA) and 3, 5-diaminobenzoic acid (DABA); the dianhydride monomer is one or a mixture of more of pyromellitic dianhydride (PMDA), 2 '-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6FDA), 4, 4' -diphenyl ether dianhydride (ODPA) and 3,3 ', 4, 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA).
Preferably, the polyamide selective layer in step (4) is prepared by the following method: soaking the polyimide nanofiber basement membrane in a water-phase monomer solution of m-phenylenediamine, taking out and removing the water-phase monomer solution on the surface layer, pouring an oil-phase monomer solution containing trimesoyl chloride on the surface of the membrane, and reacting for a period of time to prepare the polyamide selection layer.
Preferably, the concentration of the polyamic acid in the step (1) is 10 to 25 wt%.
According to another aspect of the present invention, there is provided a polyimide separation membrane resistant to polar aprotic organic solvents, prepared according to the preparation method described above.
Preferably, the gel content of the polyimide separation membrane is 98% or more.
According to another aspect of the invention, there is provided the use of a polar aprotic organic solvent resistant polyimide separation membrane in organic solvent system membrane separation.
Preferably, the organic solvent system comprises a mixture of one or more of NMP, DMF, DMAC and DMSO.
The invention has the following beneficial effects:
(1) the polyimide nanofiber separation membrane with high flux and polar aprotic organic solvent resistance is prepared by adopting a simple polyamide acid synthesis method combined with electrostatic spinning and thermal imidization, and the polyimide separation membrane prepared by the method has excellent polar aprotic organic solvent resistance.
(2) The TFC membrane prepared based on the polyimide nanofiber base membrane is used for separating polar aprotic organic solvents, has ultrahigh polar aprotic organic solvent flux, and simultaneously has excellent separation selectivity.
Drawings
FIG. 1 is a gel content chart of polyimide separation membranes prepared in examples 1 to 6.
FIG. 2 is a photograph of the polyimide separation membranes prepared in examples 3 to 6 after being soaked in a polar aprotic organic solvent (DMF) at 50 ℃ for 48 hours.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Examples
Example 1
(1) Dissolving 28.0g of 2,6-DAT monomer in 702.0g of DMF solution in a three-neck flask, introducing nitrogen for protection, adding 50.0g of PMDA monomer into the solution after the monomer is completely dissolved, continuously introducing nitrogen for protection, violently stirring, and carrying out polycondensation reaction at low temperature to prepare a 10 wt% polyamic acid solution;
(2) the prepared polyamic acid solution is prepared by an electrostatic spinning method, and the specific mode parameters of the polyamic acid nanofiber are 10kV, the temperature is 10 ℃, and the relative humidity is 20%;
(3) putting the prepared polyamic acid nanofiber membrane in a muffle furnace, introducing nitrogen at 150 ℃ and carrying out hot imidization for 0.5h to obtain a polyimide nanofiber basement membrane;
(4) firstly soaking the prepared polyimide nanofiber basement membrane in a water-phase monomer solution of m-phenylenediamine, fixing the polyimide nanofiber basement membrane in a plate frame subjected to interfacial polymerization, removing the water-phase monomer solution on the surface layer, pouring an oil-phase monomer solution containing trimesoyl chloride on the surface of the membrane, reacting for 1min to obtain a TFC membrane, and finally obtaining a polyimide separation membrane which is marked as a PI membrane 1.
Example 2
(1) Dissolving 22.5g of ODA monomer in 217.5g of DMAC solution in a three-neck flask, introducing nitrogen for protection, adding 50g of 6FDA monomer into the solution after the ODA monomer is completely dissolved, continuously introducing nitrogen for protection, violently stirring, and carrying out polycondensation reaction at low temperature to prepare a polyamic acid solution with the concentration of 25 wt%;
(2) the prepared polyamic acid solution is prepared by an electrostatic spinning method, and the specific mode parameters of the polyamic acid nanofiber are 30kV, the temperature is 60 ℃, and the relative humidity is 60%;
(3) putting the prepared polyamic acid nanofiber membrane in a muffle furnace, introducing argon at 200 ℃ and carrying out hot imidization for 10 hours to obtain a polyimide nanofiber basement membrane;
(4) firstly soaking the prepared polyimide nanofiber basement membrane in a water-phase monomer solution of m-phenylenediamine, fixing the polyimide nanofiber basement membrane in a plate frame subjected to interfacial polymerization, removing the water-phase monomer solution on the surface layer, pouring an oil-phase monomer solution containing trimesoyl chloride on the surface of the membrane, reacting for 1min to obtain a TFC membrane, and finally obtaining a polyimide separation membrane, namely a PI membrane 2.
Example 3
(1) Dissolving 32.0g of MDA monomer in 464.7g of NMP solution in a three-neck flask, introducing nitrogen for protection, adding 50.0g of OPDA monomer into the solution after the MDA monomer is completely dissolved, continuously introducing nitrogen for protection, violently stirring, and carrying out polycondensation reaction at low temperature to prepare a polyamic acid solution with the concentration of 15 wt%;
(2) the prepared polyamic acid solution is prepared by an electrostatic spinning method, and the specific mode parameters of the polyamic acid nanofiber are 20kV, the temperature is 40 ℃, and the relative humidity is 40%;
(3) placing the prepared polyamic acid nanofiber membrane in a vacuum muffle furnace, vacuumizing, and performing thermal imidization for 5 hours at the temperature of 200 ℃ to obtain a polyimide nanofiber basement membrane;
(4) firstly soaking the prepared polyimide nanofiber basement membrane in a water-phase monomer solution of m-phenylenediamine, fixing the polyimide nanofiber basement membrane in a plate frame subjected to interfacial polymerization, removing the water-phase monomer solution on the surface layer, pouring an oil-phase monomer solution containing trimesoyl chloride on the surface of the membrane, reacting for 1min to obtain a TFC membrane, and finally obtaining a polyimide separation membrane, namely a PI membrane 3.
Example 4
(1) Dissolving 23.3g of DAM monomer in 415.4g of DMF solution in a three-neck flask, introducing nitrogen for protection, adding 50g of BTDA monomer into the solution after the DAM monomer is completely dissolved, continuously introducing nitrogen for protection, violently stirring, and carrying out polycondensation reaction at low temperature to prepare 15 wt% polyamic acid solution;
(2) the prepared polyamic acid solution is prepared by an electrostatic spinning method, and the specific mode parameters of the polyamic acid nanofiber are 20kV, the temperature is 30 ℃, and the relative humidity is 50%;
(3) putting the prepared polyamic acid nanofiber membrane in a muffle furnace, introducing nitrogen at 300 ℃ and carrying out hot imidization for 5h to obtain a polyimide nanofiber basement membrane;
(4) firstly soaking the prepared polyimide nanofiber basement membrane in a water-phase monomer solution of m-phenylenediamine, fixing the polyimide nanofiber basement membrane in a plate frame subjected to interfacial polymerization, removing the water-phase monomer solution on the surface layer, pouring an oil-phase monomer solution containing trimesoyl chloride on the surface of the membrane, reacting for 1min to obtain a TFC membrane, and finally obtaining a polyimide separation membrane, namely a PI membrane 4.
Example 5
(1) Dissolving 76.6g of 6FpDA monomer in 506.4g of DMAC solution in a three-neck flask, introducing nitrogen for protection, adding 50.0g of PMDA monomer into the solution after the monomer is completely dissolved, continuously introducing nitrogen for protection, violently stirring, and carrying out polycondensation reaction at low temperature to prepare a 20 wt% polyamic acid solution;
(2) the prepared polyamic acid solution is prepared by an electrostatic spinning method, and the specific mode parameters of the polyamic acid nanofiber are 15kV, the temperature is 40 ℃, and the relative humidity is 40%;
(3) putting the prepared polyamic acid nanofiber membrane in a muffle furnace, introducing argon at 250 ℃ and carrying out thermal imidization for 2h to obtain a polyimide nanofiber basement membrane;
(4) firstly soaking the prepared polyimide nanofiber basement membrane in a water-phase monomer solution of m-phenylenediamine, fixing the polyimide nanofiber basement membrane in a plate frame subjected to interfacial polymerization, removing the water-phase monomer solution on the surface layer, pouring an oil-phase monomer solution containing trimesoyl chloride on the surface of the membrane, reacting for 1min to obtain a TFC membrane, and finally obtaining a polyimide separation membrane, namely a PI membrane 5.
Example 6
(1) Dissolving 17.1g of DABA monomer in 268.4g of NMP solution in a three-neck flask, introducing nitrogen for protection, adding 50.0g of 6FDA monomer into the solution after the DABA monomer is completely dissolved, continuously introducing nitrogen for protection, violently stirring, and carrying out polycondensation reaction at low temperature to prepare a polyamic acid solution with the concentration of 20 wt%;
(2) the prepared polyamic acid solution is prepared by an electrostatic spinning method, and the specific mode parameters of the polyamic acid nanofiber are 15kV, the temperature is 30 ℃, and the relative humidity is 50%;
(3) placing the prepared polyamic acid nanofiber membrane in a vacuum muffle furnace, vacuumizing, and performing thermal imidization for 6 hours at 300 ℃ to obtain a polyimide nanofiber basement membrane;
(4) firstly soaking the prepared polyimide nanofiber basement membrane in a water-phase monomer solution of m-phenylenediamine, fixing the polyimide nanofiber basement membrane in a plate frame subjected to interfacial polymerization, removing the water-phase monomer solution on the surface layer, pouring an oil-phase monomer solution containing trimesoyl chloride on the surface of the membrane, reacting for 1min to obtain a TFC membrane, and finally obtaining a polyimide separation membrane, namely a PI membrane 6.
Test examples
1. And (4) testing gel content. The test method comprises the following steps: the polyimide nanofiber-based film prepared in step (3) of examples 1 to 6 was cut into small pieces, and then m1 was weighed, and was immersed in a DMF solution at 50 ℃ for 48 hours, after which the film was taken out, vacuum-dried at 120 ℃ for 12 hours, and after completely dried, its weight m2 was measured, and the result of gel content was m2/m1 × 100%. The test results are shown in fig. 1.
As can be seen from fig. 1, when the temperature of thermal imidization was 150 ℃, the gel content was 0%, i.e., the polyimide nanofiber membrane prepared under these conditions was not sufficiently imidized, and the nanofiber membrane was completely dissolved in DMF. With the change of the thermal imidization condition and the use of different synthetic monomers, the gel content of the prepared polyimide nanofiber membrane reaches 98 percent, and the prepared polyimide nanofiber membrane hardly swells in a polar aprotic organic solvent.
2. And (5) testing the performance of the organic solvent resistance. The polyimide nanofiber-based film prepared in step (3) of examples 3 to 6 was cut into small pieces, weighed, immersed in a DMF solution at 50 ℃ for 48h, and tested for organic solvent resistance. The results are shown in FIG. 2.
As can be seen from fig. 2, the polyimide nanofiber-based films prepared in examples 3 to 6 hardly swell in a polar aprotic organic solvent (DMF), and the morphology of the films remains intact.
3. And (5) testing the separation performance. The polyimide separation membranes prepared in examples 3 to 6 were used to separate DMF dye solutions and tested for organic solvent resistant nanofiltration separation performance. The results are shown in Table 1.
TABLE 1 results of separation Performance of dye/DMF solution
As can be seen from Table 1, the polyimide nanofiber-based TFC membranes prepared by the method provided by the invention all have excellent organic solvent flux and high separation selectivity.
In conclusion, the polyimide nanofiber membrane with high flux and polar aprotic organic solvent resistance is successfully prepared by directly adopting a simple and green method for preparing the polyimide nanofiber membrane, the polyimide nanofiber-based TFC membrane is successfully prepared, and the polyimide nanofiber membrane has the characteristic of high flux and polar aprotic organic solvent resistance, and the application of the polyimide membrane in the field of polar aprotic organic solvent nanofiltration is greatly expanded.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. A preparation method of a polar aprotic organic solvent resistant polyimide separation membrane is characterized by comprising the following steps:
(1) adding a diamine monomer into a solvent for dissolving, and then adding a dianhydride monomer for a polycondensation reaction to obtain a polyamic acid solution; the concentration of the polyamic acid is 10-25 wt%;
(2) preparing polyamic acid nano-fiber by electrostatic spinning of polyamic acid solution;
(3) imidizing the polyamide acid nanofiber to obtain a polyimide nanofiber basement membrane;
(4) preparing a polyamide selection layer on the surface of the polyimide nanofiber basement membrane by an interfacial polymerization method to obtain a polyimide separation membrane;
wherein the imidization is thermal imidization, the thermal imidization temperature is 150-400 ℃, the time of the thermal imidization is 0.5-10h, and the thermal imidization is one of nitrogen atmosphere thermal imidization, argon atmosphere thermal imidization and vacuum thermal imidization;
the electrostatic spinning voltage is 10-30kV, the temperature is 10-60 ℃, and the relative humidity is 20-60%.
2. The method according to claim 1, wherein the diamine monomer is one or more selected from the group consisting of 2, 6-diaminotoluene, 4 ' -diaminodiphenyl ether, 4 ' -diaminodiphenylmethane, 2,4, 6-trimethyl-1, 3-phenylenediamine, 4 ' -mono (hexafluoroisopropylidene) diphenylamine and 3, 5-diaminobenzoic acid; the dianhydride monomer is one or more of pyromellitic dianhydride, 2 '-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 4, 4' -diphenyl ether dianhydride and 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride.
3. The method according to claim 1, wherein the polyamide selective layer in the step (4) is prepared by: soaking the polyimide nanofiber basement membrane in a water-phase monomer solution of m-phenylenediamine, taking out and removing the water-phase monomer solution on the surface layer, pouring an oil-phase monomer solution containing trimesoyl chloride on the surface of the membrane, and reacting to prepare the polyamide selective layer.
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