CN111318174A - Method for preparing block copolymer hollow fiber membrane based on selective swelling method - Google Patents
Method for preparing block copolymer hollow fiber membrane based on selective swelling method Download PDFInfo
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- CN111318174A CN111318174A CN202010126875.1A CN202010126875A CN111318174A CN 111318174 A CN111318174 A CN 111318174A CN 202010126875 A CN202010126875 A CN 202010126875A CN 111318174 A CN111318174 A CN 111318174A
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- 239000012510 hollow fiber Substances 0.000 title claims abstract description 120
- 239000012528 membrane Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 50
- 230000008961 swelling Effects 0.000 title claims abstract description 37
- 229920001400 block copolymer Polymers 0.000 title claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920000469 amphiphilic block copolymer Polymers 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 16
- 238000002074 melt spinning Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 58
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 48
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 239000012046 mixed solvent Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000002202 Polyethylene glycol Substances 0.000 claims description 25
- 229920002492 poly(sulfone) Polymers 0.000 claims description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002798 polar solvent Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 8
- 229920000885 poly(2-vinylpyridine) Polymers 0.000 claims description 8
- 229920002246 poly[2-(dimethylamino)ethyl methacrylate] polymer Polymers 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- QFDBXPKKSDSURA-UHFFFAOYSA-N oxolane;propan-1-ol Chemical compound CCCO.C1CCOC1 QFDBXPKKSDSURA-UHFFFAOYSA-N 0.000 claims description 2
- QQOFJYQTBCFNNT-UHFFFAOYSA-N propan-1-ol;propan-2-one Chemical compound CCCO.CC(C)=O QQOFJYQTBCFNNT-UHFFFAOYSA-N 0.000 claims description 2
- OKDOZOFJAUITTD-UHFFFAOYSA-N propan-1-ol;toluene Chemical compound CCCO.CC1=CC=CC=C1 OKDOZOFJAUITTD-UHFFFAOYSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000003860 storage Methods 0.000 abstract description 3
- 230000004907 flux Effects 0.000 description 12
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 11
- 229940098773 bovine serum albumin Drugs 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 238000002145 thermally induced phase separation Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 230000000322 hemodialysis Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
Images
Classifications
-
- 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
- B01D69/08—Hollow fibre membranes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61M—DEVICES FOR INTRODUCING MEDIA INTO, OR ONTO, THE BODY; DEVICES FOR TRANSDUCING BODY MEDIA OR FOR TAKING MEDIA FROM THE BODY; DEVICES FOR PRODUCING OR ENDING SLEEP OR STUPOR
- A61M1/00—Suction or pumping devices for medical purposes; Devices for carrying-off, for treatment of, or for carrying-over, body-liquids; Drainage systems
- A61M1/14—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis
- A61M1/16—Dialysis systems; Artificial kidneys; Blood oxygenators ; Reciprocating systems for treatment of body fluids, e.g. single needle systems for hemofiltration or pheresis with membranes
- A61M1/1621—Constructional aspects thereof
- A61M1/1623—Disposition or location of membranes relative to fluids
-
- 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
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention provides a method for preparing a block copolymer hollow fiber membrane based on selective swelling, which comprises the following steps: an amphiphilic block copolymer is taken as a film forming material, and a compact hollow fiber is prepared by melt spinning; immersing the obtained hollow fiber in a swelling agent, and treating for 0-5h under the water bath heating of 55-70 ℃; and immediately taking out and drying after the treatment is finished to obtain the hollow fiber membrane with the bicontinuous open pore structure. The method combines melt spinning and selective swelling, only a small amount of solvent is needed to prepare the hollow fiber membrane, and the solvent can be repeatedly used, so that the influence on the environment is reduced; the method has universality and can be widely applied to the process of preparing hollow fiber membranes by various block copolymers; the prepared hollow fiber membrane can be stored in a dry state, so that the storage and transportation cost is reduced.
Description
Technical Field
The invention belongs to the technical field of porous material separation membranes, and particularly relates to a method for preparing a block copolymer hollow fiber membrane based on a selective swelling method.
Background
The hollow fiber membrane is a membrane material which is fibrous in appearance and has a self-supporting function. The hollow fiber membrane has the advantages of large packing density in unit volume, simple operation, stable structure and the like, so the hollow fiber membrane is widely applied to the aspects of water treatment, catalytic reaction, food processing, biotechnology, medical technology and the like.
At present, the methods for preparing the hollow fiber membrane by using the high polymer materials are mainly 3, which are respectively as follows: melt spinning-drawing (MSCS), Thermally Induced Phase Separation (TIPS), and non-solvent induced phase separation (NIPS). The MSCS method comprises melting high molecular material at high temperature, extruding under high stress, drawing the platelet structure of the high molecular material arranged perpendicular to the extrusion direction by subsequent cold and hot stretching to form microporous structure, and fixing the pore channel structure by heat setting process. The pore-forming operation of the method has high difficulty in regulating and controlling the pore structure, the pore size distribution is wide, and the method has less materials. The TIPS method is to mix a high molecular material with a diluent (a high boiling point small molecular compound) to form a homogeneous solution at a high temperature, to induce phase separation by cooling after spinning, to remove the diluent by extraction, etc., to obtain a hollow fiber membrane having a microporous structure. Although the TIPS method widens the range of polymer materials, it has high process requirements and easily forms a dense skin layer during the extrusion of hollow fibers, thereby causing the degradation of membrane properties. The NIPS method is that high molecular material is dissolved in organic solvent to form homogeneous solution, which is extruded out through a spinneret orifice and phase separated after certain volatilization time or direct immersion in coagulating bath to form hollow fiber membrane structure. The hollow fiber membrane prepared by the NIPS method has poor mechanical property and is easy to break in the preparation or use process. In addition, the TIPS method and the NIPS method often use a large amount of organic reagents as diluents or solvents in the preparation process, and the organic reagents need to be recovered, separated and recycled, which is very easy to cause environmental pollution.
In patents CN102764600A and CN106674580A, methods for preparing a porous membrane of a block copolymer by selective swelling are provided, and although this method can prepare a block copolymer membrane excellent in performance, it is difficult to scale up the production, and the prepared membrane is a block copolymer flat membrane and is limited in practical application.
Therefore, a simple, efficient and environmentally friendly method for preparing hollow fiber membranes was developed in this patent based on selective swelling.
Disclosure of Invention
To overcome the drawbacks and disadvantages of the prior art, the present invention proposes a method for preparing a hollow fiber membrane by combining melt spinning and selective swelling. The method can prepare the hollow fiber membrane by only using a small amount of solvent, and can continuously regulate and control the pore structure and the performance of the hollow fiber membrane by simply regulating the swelling condition.
The technical scheme for realizing the aim of the invention is as follows:
a method of making a hollow fiber membrane by melt spinning-selective swelling comprising:
1) an amphiphilic block copolymer is taken as a film forming material, and a compact hollow fiber is prepared by melt spinning;
2) immersing the hollow fiber obtained in the step 1) in a swelling agent, and treating for 0-5h under the heating of a water bath at the temperature of 55-70 ℃. Immediately taking out the hollow fiber after the treatment is finished, and drying at a certain temperature to obtain a hollow fiber membrane with a bicontinuous pore-opening structure;
in the embodiment of the present invention, the amphiphilic block copolymer of step 1) is composed of a block a and a block B (a-B), wherein the block a is selected from any one of Polysulfone (PSF) or Polystyrene (PS), the block B is selected from any one of polyethylene glycol (PEG), polyethylene oxide (PEO), poly (2-vinylpyridine) (P2VP) or poly N, N-dimethylaminoethyl methacrylate (PDMAEMA), and the total molecular weight of the amphiphilic block copolymer is 5-20 kilodalton; preferably, the block a is Polysulfone (PSF) and the block B is polyethylene glycol (PEG).
In a further preferred embodiment of the present invention, the amphiphilic block copolymer and the molecular weight thereof are PSF75-PEG20、PS55-P2VP18.5Or PS124.2-PDMAEMA23.6In kilodaltons.
In the embodiment of the present invention, the melt spinning in step 1) is preferably performed by melting the solid amphiphilic block copolymer, and then using a single-screw or twin-screw extruder to form the hollow fiber through a spinneret.
In a more preferred embodiment of the present invention, the melting temperature is 100-.
In a more preferred embodiment of the present invention, the size of the spinneret is between 0.5/0.28/0.15mm and 1.4/0.9/0.6 mm.
In the scheme of the invention, the swelling agent in the step 2) is an alcohol solvent, a mixed solvent of the alcohol solvent and a polar solvent or a carboxylic acid solvent.
In a further preferred embodiment, the alcohol solvent may be selected from any one or a combination of two or more of methanol, ethanol, n-propanol, butanol, isopropanol, ethylene glycol, and glycerol; ethanol or n-propanol are most preferred.
In a further preferred embodiment, the polar solvent may be selected from acetone, toluene or tetrahydrofuran; most preferred is acetone or toluene.
In a further preferred embodiment, the carboxylic acid solvent may be selected from formic acid, acetic acid, propionic acid or butyric acid; acetic acid is most preferred.
In a preferred embodiment of the invention, the swelling agent is a mixed solvent composed of ethanol or n-propanol and a polar solvent, and the polar solvent accounts for 0-50 wt% of the mixed solvent; more preferably, the polar solvent accounts for 10-25 wt% of the mixed solvent; the polar solvent is further preferably any one of acetone, tetrahydrofuran or toluene, namely a mixed solvent of n-propanol and acetone, a mixed solvent of n-propanol and tetrahydrofuran or a mixed solvent of n-propanol and toluene; most preferred is an n-propanol acetone mixed solvent containing 20 wt% of acetone, an n-propanol tetrahydrofuran mixed solvent containing 20 wt% of tetrahydrofuran, or an n-propanol toluene mixed solvent containing 20 wt% of toluene.
In a preferred embodiment of the present invention, the swelling temperature in step 2) is preferably 55 ℃, 60 ℃, 65 ℃ or 70 ℃; the swelling time is preferably 1h, 2h or 3 h; in a further preferred embodiment, the swelling temperature in step 2) is 65 ℃ and the swelling time is 1 h.
The invention relates to a preferable embodiment, which comprises the following specific steps:
1) melt spinning process
Heating and melting the solid block copolymer at high temperature to obtain molten polymer, and preparing the molten polymer into the hollow fiber by a single-screw or double-screw extruder through a spinneret; the amphiphilic block copolymer consists of a block A and a block B (A-B), wherein the block A is selected from any one of Polysulfone (PSF) or Polystyrene (PS), and the block B is selected from any one of polyethylene glycol (PEG), polyethylene oxide (PEO), poly (2-vinylpyridine) (P2VP) or poly N, N-dimethylaminoethyl methacrylate (PDMAEMA); wherein the percentage of the block B in the total mass of the amphiphilic block copolymer is 10-40%; the total molecular weight of the amphiphilic block copolymer is 5-20 ten thousand daltons;
2) selective swelling aperturing process
Placing the amphiphilic block copolymer hollow fiber obtained in the step 1) into a container filled with a swelling agent, immediately placing the container in a water bath heating environment at 55-70 ℃ for treatment for 0-5h, thereby generating an open pore structure, and then drying at a certain temperature to obtain the amphiphilic block copolymer hollow fiber membrane with a bicontinuous porous structure.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) by combining melt spinning and selective swelling, the problem that a large amount of organic solvent is used in the process of preparing the hollow fiber membrane is solved, and potential environmental pollution is avoided.
In the prior art, a large amount of organic solvent is often used in the preparation of a casting solution in the process of preparing a hollow fiber membrane by a TIPS or NIPS method, and the use of an organic reagent can lead to a large amount of subsequent treatment processes in industry, such as separation, recovery and the like. The subsequent treatment steps are not only complicated and increase the production cost, but also easily cause environmental pollution. The invention prepares the hollow fiber through the melt spinning process, and melts the high molecular material at high temperature, thereby spinning, and avoiding the use of organic reagents. Although a small amount of organic reagent can be used in the subsequent selective swelling process, the organic reagent can be reused only by taking out the treated hollow fiber membrane without a separation and recovery process.
(2) The performance of the hollow fiber membrane can be adjusted in a large range to meet different use requirements by simply regulating and controlling selective swelling conditions.
In the prior art, the structure, the appearance and the performance of the pore channel are difficult to adjust. The invention can continuously adjust the performance of the hollow fiber membrane in a large range by simply adjusting the selective swelling process, such as the composition of a swelling agent, the swelling temperature and the swelling time, and simultaneously, the shape and the pore structure of the membrane can also be adjusted.
(3) The hollow fiber membrane prepared by the method can be directly stored in a dry state, so that bacteria are not easy to breed in the storage process, the transportation and storage cost is reduced, and the method is favorable for preparing the hemodialysis membrane subsequently;
(4) the preparation process is simple, and the hydrophilic block can be spontaneously enriched on the surface and the pore wall of the membrane in the selective swelling process, so that the hydrophilicity and the flux performance of the hollow fiber membrane can be improved.
Drawings
FIG. 1 is an SEM image of the porous structure of the outer surface of the hollow-fiber membrane of the block copolymer obtained in example 1;
FIG. 2 is an SEM photograph of the inner surface porous structure of the hollow fiber membrane of the block copolymer obtained in example 1;
FIG. 3 is a SEM image of a cross-sectional porous structure of a block copolymer hollow fiber membrane obtained in example 1;
FIG. 4 is an SEM image of the porous structure of the outer surface of the hollow-fiber membrane of the block copolymer obtained in example 10;
FIG. 5 is an SEM photograph of the inner surface porous structure of the hollow-fiber membrane of the block copolymer obtained in example 10;
FIG. 6 is an SEM image of the cross-sectional porous structure of the hollow-fiber block copolymer membrane obtained in example 10.
Detailed Description
The present invention will be further explained with reference to examples. The following examples are provided only for illustrating the present invention and are not intended to limit the scope of the present invention.
Example 1.
20g of PSF75-PEG20The block copolymer is added into a double-screw extruder, melted at 170/180 ℃, extruded through a spinneret with the size of 0.5/0.28/0.15mm at 170 ℃, and naturally cooled to obtain the hollow fiber. The resulting hollow fiber was immersed in a mixed solvent of n-propanol and acetone containing 20 wt% of acetone, and treated in a water bath at 65 ℃ for 1 hour. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
Fig. 1, fig. 2 and fig. 3 are SEM images of the inner and outer surfaces and the cross section of the polysulfone/polyethylene glycol hollow fiber membrane, respectively, as follows: the inner surface and the outer surface of the hollow fiber membrane are all of good open pore structures, and the pore structure penetrates through the whole membrane layer. The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 65 L.m-2·h-1·bar-1The bovine serum albumin retention rate is about 60%.
Example 2
20g of PSF75-PEG20Adding the block copolymer into a double-screw extruder, melting at 170/180 ℃, extruding at 170 ℃ through a spinneret with the size of 0.8/0.4/0.2mm, and naturally cooling to obtain the hollow fiber. The resulting hollow fiber was immersed in a mixed solvent of n-propanol and acetone containing 20 wt% of acetone, and treated in a water bath at 65 ℃ for 1 hour. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 50 L.m-2·h-1·bar-1The bovine serum albumin retention rate was about 24%.
Example 3
20g of PSF75-PEG20The block copolymer is added into a double-screw extruder, melted at 170/180 ℃, extruded by a spinneret with the size of 1.4/0.9/0.6mm at 170 ℃, and naturally cooled to obtain the hollow fiber. The resulting hollow fiber was immersed in a mixed solvent of n-propanol and acetone containing 20 wt% of acetone, and treated in a water bath at 65 ℃ for 1 hour. After the treatment is finishedThe hollow fiber was immediately taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 40 L.m-2·h-1·bar-1The bovine serum albumin retention rate was about 21%.
Example 4
20g of PSF75-PEG20The block copolymer is added into a double-screw extruder, melted at 170/180 ℃, extruded through a spinneret with the size of 0.5/0.28/0.15mm at 170 ℃, and naturally cooled to obtain the hollow fiber. The resulting hollow fiber was immersed in a mixed solvent of n-propanol and acetone containing 20 wt% of acetone, and treated in a water bath at 55 ℃ for 1 hour. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 15 L.m-2·h-1·bar-1The bovine serum albumin retention rate is about 90%.
Example 5
20g of PSF75-PEG20The block copolymer is added into a double-screw extruder, melted at 170/180 ℃, extruded through a spinneret with the size of 0.5/0.28/0.15mm at 170 ℃, and naturally cooled to obtain the hollow fiber. The obtained hollow fiber was immersed in a mixed solvent of n-propanol and acetone containing 20 wt% of acetone, and treated in a water bath at 60 ℃ for 1 hour. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 45 L.m-2·h-1·bar-1The bovine serum albumin retention was about 65%.
Example 6
20g of PSF75-PEG20The block copolymer is added into a double-screw extruder, melted at 170/180 ℃, extruded through a spinneret with the size of 0.5/0.28/0.15mm at 170 ℃, and naturally cooled to obtain the hollow fiber. Immersing the resulting hollow fiber in a solution containing 20 wt% acetoneTreating in a mixed solvent of n-propanol and acetone in a water bath at 70 ℃ for 1 h. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 120 L.m-2·h-1·bar-1The bovine serum albumin retention rate was about 30%.
Example 7
20g of PSF75-PEG20The block copolymer is added into a double-screw extruder, melted at 170/180 ℃, extruded through a spinneret with the size of 0.5/0.28/0.15mm at 170 ℃, and naturally cooled to obtain the hollow fiber. The resulting hollow fiber was immersed in a mixed solvent of n-propanol and acetone containing 20 wt% of acetone, and treated in a water bath at 65 ℃ for 2 hours. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 85 L.m-2·h-1·bar-1The bovine serum albumin retention rate was about 40%.
Example 8
20g of PSF75-PEG20The block copolymer is added into a double-screw extruder, melted at 170/180 ℃, extruded through a spinneret with the size of 0.5/0.28/0.15mm at 170 ℃, and naturally cooled to obtain the hollow fiber. The resulting hollow fiber was immersed in a mixed solvent of n-propanol and acetone containing 20 wt% of acetone, and treated in a water bath at 65 ℃ for 3 hours. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 125 L.m-2·h-1·bar-1The bovine serum albumin retention rate was about 20%.
Example 9
20g of PSF75-PEG20Adding the block copolymer into a twin-screw extruder, melting at 170/180 deg.C, extruding at 170 deg.C through a spinneret with size of 0.5/0.28/0.15mm, and naturally coolingThen obtaining the hollow fiber. The resulting hollow fiber was immersed in a mixed solvent of n-propanol and acetone containing 20 wt% of acetone, and treated in a water bath at 65 ℃ for 5 hours. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 120 L.m-2·h-1·bar-1The bovine serum albumin retention rate was about 22%.
Example 10
20g of PSF75-PEG20Adding the block copolymer into a double-screw extruder, melting at 170/180 ℃, extruding at 170 ℃ through a spinneret with the size of 0.8/0.4/0.2mm, and naturally cooling to obtain the hollow fiber. The obtained hollow fiber was immersed in a mixed solvent of n-propanol and tetrahydrofuran containing 20 wt% of tetrahydrofuran, and treated in a water bath at 65 ℃ for 1 hour. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
Fig. 4, fig. 5 and fig. 6 are SEM images of the inner and outer surfaces and the cross section of the polysulfone/polyethylene glycol hollow fiber membrane, respectively, as follows: the inner surface and the outer surface of the hollow fiber membrane are all of good open pore structures, and the pore structure penetrates through the whole membrane layer. The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 140 L.m-2·h-1·bar-1The bovine serum albumin retention rate was about 10%.
Example 11
20g of PSF75-PEG20Adding the block copolymer into a double-screw extruder, melting at 170/180 ℃, extruding at 170 ℃ through a spinneret with the size of 0.8/0.4/0.2mm, and naturally cooling to obtain the hollow fiber. The resulting hollow fiber was immersed in a mixed solvent of n-propanol and toluene containing 10 wt% of toluene and treated in a water bath at 65 ℃ for 1 hour. Immediately after the treatment, the hollow fiber was taken out and dried at 40 ℃ to obtain a hollow fiber membrane.
The prepared polysulfone/polyethylene glycol hollow fiber membrane has the pure water flux of 150 L.m-2·h-1·bar-1On the other hand, the bovine serum albumin retention rate isAbout 21 percent.
Example 12
20g of PS124.2-PDMAEMA23.6The block copolymer is added into a double-screw extruder, melted at 100/110 ℃, extruded by a spinneret with the size of 1.4/0.9/0.6mm at 100 ℃, and naturally cooled to obtain the hollow fiber. Immersing the obtained hollow fiber in an ethanol solvent, treating in a water bath at 70 ℃ for 2h, and drying at room temperature to obtain the hollow fiber membrane.
Example 13
20gPS124.2-PDMAEMA23.6The block copolymer is added into a double-screw extruder, melted at 140/150 ℃, extruded through a spinneret with the size of 1.4/0.9/0.6mm at 145 ℃, and naturally cooled to obtain the hollow fiber. Immersing the obtained hollow fiber in an ethanol solvent, treating in a water bath at 70 ℃ for 2h, and drying at room temperature to obtain the hollow fiber membrane.
Example 14
20g of PSF75-PEG20The block copolymer is added into a double-screw extruder, melted at 200/210 ℃, extruded by a spinneret with the size of 1.4/0.9/0.6mm at 200 ℃, and naturally cooled to obtain the hollow fiber.
Claims (10)
1. A method for preparing a block copolymer hollow fiber membrane based on selective swelling, comprising:
1) an amphiphilic block copolymer is taken as a film forming material, and a compact hollow fiber is prepared by melt spinning;
2) immersing the hollow fiber obtained in the step 1) in a swelling agent, and treating for 0-5h under the heating of water bath at the temperature of 55-70 ℃; and immediately taking out the hollow fiber after the treatment is finished, and drying to obtain the hollow fiber membrane with the bicontinuous open pore structure.
2. The method of claim 1, wherein: 1) the amphiphilic block copolymer consists of a block A and a block B (A-B), wherein the block A is selected from any one of Polysulfone (PSF) or Polystyrene (PS), the block B is selected from any one of polyethylene glycol (PEG), polyethylene oxide (PEO), poly (2-vinylpyridine) (P2VP) or poly N, N-dimethylaminoethyl methacrylate (PDMAEMA), and the total molecular weight of the amphiphilic block copolymer is 5-20 kilodalton; preferably, the block a is Polysulfone (PSF) and the block B is polyethylene glycol (PEG).
3. The method of claim 2, wherein: the amphiphilic block copolymer and the molecular weight thereof are PSF75-PEG20、PS55-P2VP18.5Or PS124.2-PDMAEMA23.6In kilodaltons.
4. The method of claim 1, wherein: the melt spinning in the step 1) is to melt the solid amphiphilic block copolymer and then use a single-screw or double-screw extruder to prepare the hollow fiber through a spinneret.
5. The method of claim 4, wherein: the melting temperature is 100-210 ℃, preferably 170-180 ℃.
6. The method of claim 1, wherein: the swelling agent in the step 2) is an alcohol solvent, a mixed solvent of the alcohol solvent and a polar solvent, or a carboxylic acid solvent.
7. The method of claim 6, wherein: the alcohol solvent is selected from one or more of methanol, ethanol, n-propanol, butanol, isopropanol, ethylene glycol and glycerol; preferably ethanol or n-propanol; the polar solvent is selected from any one or a composition of more than two of acetone, toluene or tetrahydrofuran; preferably acetone or toluene; the carboxylic acid solvent is selected from any one or a mixture of more than two of formic acid, acetic acid, propionic acid or butyric acid; acetic acid is preferred.
8. The method of claim 6, wherein: the mixed solvent of the alcohol solvent and the polar solvent is ethanol or a mixed solvent composed of n-propanol and the polar solvent, and the polar solvent accounts for 0-50 wt% of the mixed solvent; more preferably, the polar solvent accounts for 10-25 wt% of the mixed solvent; the polar solvent is further preferably any one of acetone, tetrahydrofuran or toluene, namely a mixed solvent of n-propanol and acetone, a mixed solvent of n-propanol and tetrahydrofuran or a mixed solvent of n-propanol and toluene; most preferred is an n-propanol acetone mixed solvent containing 20 wt% of acetone, an n-propanol tetrahydrofuran mixed solvent containing 20 wt% of tetrahydrofuran, or an n-propanol toluene mixed solvent containing 20 wt% of toluene.
9. The method of claim 1, wherein: the swelling temperature of the step 2) is 55 ℃, 60 ℃, 65 ℃ or 70 ℃; the swelling time is 1h, 2h or 3 h; in a further preferred embodiment, the swelling temperature in step 2) is 65 ℃ and the swelling time is 1 h.
10. The method of claim 1, characterized by the specific steps of:
1) melt spinning process
Heating and melting the solid block copolymer at high temperature to obtain molten polymer, and preparing the molten polymer into the hollow fiber by a single-screw or double-screw extruder through a spinneret; the amphiphilic block copolymer consists of a block A and a block B (A-B), wherein the block A is selected from any one of Polysulfone (PSF) or Polystyrene (PS), and the block B is selected from any one of polyethylene glycol (PEG), polyethylene oxide (PEO), poly (2-vinylpyridine) (P2VP) or poly N, N-dimethylaminoethyl methacrylate (PDMAEMA); wherein the percentage of the block B in the total mass of the amphiphilic block copolymer is 10-40%; the total molecular weight of the amphiphilic block copolymer is 5-20 ten thousand daltons;
2) selective swelling aperturing process
Placing the amphiphilic block copolymer hollow fiber obtained in the step 1) into a container filled with a swelling agent consisting of n-propanol and a polar solvent, immediately placing the container in a water bath heating environment at 55-70 ℃ for treatment for 0-5h to generate an open pore structure, and then drying at a certain temperature to obtain the amphiphilic block copolymer hollow fiber membrane with the bicontinuous porous structure.
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| CN113041853A (en) * | 2021-03-24 | 2021-06-29 | 南京工业大学 | Anti-pollution ultrafiltration membrane based on zwitterion and preparation method and application thereof |
| CN113041848A (en) * | 2021-03-24 | 2021-06-29 | 南京工业大学 | Method for preparing block copolymer hollow fiber membrane by combining selective swelling and melt-spinning stretching method |
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| CN106674580A (en) * | 2017-01-04 | 2017-05-17 | 南京工业大学 | Preparation method of polysulfone nano porous polymer |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113041853A (en) * | 2021-03-24 | 2021-06-29 | 南京工业大学 | Anti-pollution ultrafiltration membrane based on zwitterion and preparation method and application thereof |
| CN113041848A (en) * | 2021-03-24 | 2021-06-29 | 南京工业大学 | Method for preparing block copolymer hollow fiber membrane by combining selective swelling and melt-spinning stretching method |
| WO2022199592A1 (en) * | 2021-03-24 | 2022-09-29 | 南京工业大学 | Method for preparing block copolymer hollow fiber membrane by combining selective swelling and melt spinning and stretching method |
| US11766640B2 (en) | 2021-03-24 | 2023-09-26 | Nanjing Tech University | Method for preparing block copolymer hollow fiber membrane by melt spinning-stretching and selective swelling |
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