CN118788161B - Polyether sulfone membrane with highly asymmetric structure and preparation method and application thereof - Google Patents
Polyether sulfone membrane with highly asymmetric structure and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 121
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 76
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005266 casting Methods 0.000 claims abstract description 68
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000007788 liquid Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 13
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 12
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 12
- 238000005345 coagulation Methods 0.000 claims abstract description 7
- 230000015271 coagulation Effects 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims description 26
- 230000001112 coagulating effect Effects 0.000 claims description 25
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 9
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- 229920001661 Chitosan Polymers 0.000 claims description 5
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 claims description 4
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 claims description 4
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 claims description 4
- RBNPOMFGQQGHHO-UHFFFAOYSA-N glyceric acid Chemical compound OCC(O)C(O)=O RBNPOMFGQQGHHO-UHFFFAOYSA-N 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 238000011100 viral filtration Methods 0.000 claims description 4
- 229920002307 Dextran Polymers 0.000 claims description 3
- FZWBNHMXJMCXLU-BLAUPYHCSA-N isomaltotriose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1OC[C@@H]1[C@@H](O)[C@H](O)[C@@H](O)[C@@H](OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O)O1 FZWBNHMXJMCXLU-BLAUPYHCSA-N 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 239000007888 film coating Substances 0.000 claims 1
- 238000009501 film coating Methods 0.000 claims 1
- 238000000108 ultra-filtration Methods 0.000 abstract description 43
- 241000700605 Viruses Species 0.000 abstract description 19
- 239000002131 composite material Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000013341 scale-up Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 55
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 27
- 239000010410 layer Substances 0.000 description 24
- 239000011148 porous material Substances 0.000 description 24
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 238000002791 soaking Methods 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 239000011521 glass Substances 0.000 description 10
- 239000003960 organic solvent Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 238000007790 scraping Methods 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000005191 phase separation Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012460 protein solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- 241000709749 Pseudomonas phage PP7 Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000008055 phosphate buffer solution Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000010254 subcutaneous injection Methods 0.000 description 1
- 239000007929 subcutaneous injection Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/14—Extraction; Separation; Purification
- C07K1/34—Extraction; Separation; Purification by filtration, ultrafiltration or reverse osmosis
-
- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N7/00—Viruses; Bacteriophages; Compositions thereof; Preparation or purification thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Genetics & Genomics (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Biochemistry (AREA)
- Wood Science & Technology (AREA)
- General Health & Medical Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Medicinal Chemistry (AREA)
- Zoology (AREA)
- General Engineering & Computer Science (AREA)
- Microbiology (AREA)
- Virology (AREA)
- Biotechnology (AREA)
- Biomedical Technology (AREA)
- Immunology (AREA)
- Analytical Chemistry (AREA)
- Biophysics (AREA)
- Molecular Biology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
本发明提供了一种高度非对称结构的聚醚砜膜及其制备方法和应用，涉及材料技术领域。本发明提供的高度非对称结构的聚醚砜膜的制备方法，包括：将铸膜液涂敷成液膜，然后将液膜浸入凝固浴中固化成膜，再经水洗后制备得到高度非对称结构的聚醚砜膜。该制备方法工艺简单，仅通过一种铸膜液进行制备，一体成型，不需要多层复合制备工艺，易于放大；通过调控铸膜液配方和工艺参数控制聚醚砜膜的选择分离层和多孔支撑层结构，进而获得具有不同非对称结构的聚醚砜膜，为减弱超滤膜的Trade‑off效应提供了新思路；制备得到的聚醚砜膜可应用于蛋白质或病毒的分离纯化，满足实际应用需求。
The present invention provides a polyethersulfone membrane with a highly asymmetric structure and a preparation method and application thereof, and relates to the field of material technology. The preparation method of the polyethersulfone membrane with a highly asymmetric structure provided by the present invention comprises: applying a casting liquid into a liquid film, then immersing the liquid film in a coagulation bath to solidify into a film, and then washing with water to prepare a polyethersulfone membrane with a highly asymmetric structure. The preparation method has a simple process, is prepared by only one casting liquid, is integrally formed, does not require a multi-layer composite preparation process, and is easy to scale up; the selective separation layer and porous support layer structure of the polyethersulfone membrane are controlled by regulating the casting liquid formula and process parameters, thereby obtaining a polyethersulfone membrane with different asymmetric structures, which provides a new idea for reducing the Trade-off effect of the ultrafiltration membrane; the prepared polyethersulfone membrane can be applied to the separation and purification of proteins or viruses to meet the needs of practical applications.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a polyether sulfone membrane with a highly asymmetric structure, and a preparation method and application thereof.
Background
Polyether sulfone (PES) polymer materials are widely used for preparing ultrafiltration membranes by virtue of excellent chemical inertness, thermodynamic stability, mechanical strength and other performances, and are further applied to separation and purification in the fields of biology and medical treatment. However, the permeation selective separation performance of ultrafiltration membranes is mainly affected by the membrane pore size and membrane structure. In order to obtain the ultrafiltration membrane with both high flux and high retention rate, the highly asymmetric membrane with compact surface and porous bottom is one of research hot spots in the current membrane separation field. In addition, the protein solution from which viruses are removed is concentrated by utilizing the pore diameter of the cortex of the ultrafiltration membrane so as to meet the concentration requirement of the subcutaneous injection agent. Therefore, although the traditional finger Kong Chaolv membrane has good permeability, the bottom of the membrane is of a large cavity structure, so that the membrane has no advantages in biological safety and mechanical strength, while the spongy pore structure has the characteristics of gradient pore structure and excellent pressure resistance, but the structure is often limited by the compact cortex of the ultrafiltration membrane, so that the prepared membrane has small asymmetry in structure and has the defects of low flux and low loading. Therefore, the ultrafiltration membrane which has high asymmetry and adjustable and controllable membrane aperture gradient change has great practical application value.
The common ultrafiltration membrane preparation method at present is a membrane integrally prepared after single-layer casting, but the asymmetric structure of the prepared membrane is not obvious. In order to prepare an ultrafiltration membrane with a highly asymmetric structure, an asymmetric composite ultrafiltration membrane with a multi-layer structure is disclosed in Chinese patent CN1759924B, CN116747721A, CN117282280B, wherein the composite ultrafiltration membrane is prepared by at least two different casting solutions, and different membrane liquid layers are required to be scraped sequentially by adopting a slot die coater for co-casting or adjusting the thickness of a scraper in the preparation process. Although the composite ultrafiltration membrane with the separation layer and the support layer which have the filtration accuracy and the filtration flow rate can be prepared by adopting the technology. But the technology has the very obvious defects of easy layering among different layers, easy generation of a skin layer between layers, obvious boundary lines, more complicated phase separation process and difficult control of the process in the process of preparing the film.
In view of this, the present invention has been made.
Disclosure of Invention
The first objective of the present invention is to provide a method for preparing a polyethersulfone membrane with a highly asymmetric structure, so as to solve the above technical problems.
A second object of the present invention is to provide a polyethersulfone membrane of highly asymmetric structure.
A third object of the present invention is to provide the use of the above-mentioned polyethersulfone membranes of highly asymmetric structure for protein or virus filtration.
In order to achieve the above object, the following technical scheme is adopted:
in a first aspect, the present invention provides a method for preparing a polyethersulfone membrane having a highly asymmetric structure, comprising the steps of:
Coating the casting solution into a liquid film, immersing the liquid film into a coagulating bath for curing to form a film, and washing with water to obtain a polyether sulfone film with a highly asymmetric structure;
The film casting solution comprises, by mass, 15% -20% of polyethersulfone, 40% -60% of a non-solvent and the balance of a good solvent;
The non-solvent is at least one of glycerol ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether;
the good solvent comprises at least one of N-N dimethylformamide, N-N dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide;
the coagulating bath comprises a good solvent and water, wherein the mass ratio of the good solvent is 10% -70%, and the temperature of the coagulating bath is 20-50 ℃.
As a further technical scheme, the casting solution further comprises a hydrophilic additive.
As a further technical scheme, the hydrophilic additive comprises at least one of polyvinylpyrrolidone, polyethylene glycol, chitosan, polyvinyl alcohol, dextran, lithium chloride or lithium perchlorate.
As a further technical scheme, the mass ratio of the hydrophilic additive in the casting film liquid is less than or equal to 4%.
As a further technical solution, a doctor blade is used to coat the carrier with a liquid film.
As a further technical scheme, in the process of coating the liquid film, the temperature of the environment is 20-25 ℃ and the humidity is 40-70 RH%.
As a further technical scheme, the time for immersing the liquid film in the coagulating bath is 1-10 min.
In a second aspect, the invention provides a polyether sulfone membrane with a highly asymmetric structure, which is prepared by the preparation method.
As a further technical scheme, the polyethersulfone membrane comprises a selective separation layer and a porous support layer;
the thickness of the separation layer is selected to be 200-500 nm;
The thickness of the polyethersulfone film is 100-150 mu m.
In a third aspect, the present invention provides the use of a polyethersulfone membrane of the highly asymmetric structure described above in protein or viral filtration.
Compared with the prior art, the invention has the following beneficial effects:
The preparation method of the polyether sulfone membrane with the highly asymmetric structure is simple in process, is prepared by only one casting solution, is integrally formed, does not need a multi-layer composite preparation process, is easy to amplify, controls the structure of a selective separation layer and a porous support layer of the polyether sulfone membrane by regulating and controlling the formulation and the process parameters of the casting solution, further obtains the polyether sulfone membrane with different asymmetric structures, provides a new thought for weakening the Trade-off effect of an ultrafiltration membrane, and can be applied to separation and purification of proteins or viruses, thereby meeting the actual application requirements.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a cross-sectional view of the PES ultrafiltration membrane provided in example 1 of the present invention, at 5000X magnification;
FIG. 2 is a cross-sectional view of the PES ultrafiltration membrane provided in comparative example 1, at 1000X magnification;
FIG. 3 is a cross-sectional view of the PES ultrafiltration membrane provided in comparative example 2, at 1000X magnification;
FIG. 4 is a cross-sectional view of the PES ultrafiltration membrane provided by example 2 of the present invention, at a magnification of 2000X;
FIG. 5 is a surface electron microscope image of the PES ultrafiltration membrane supporting layer provided in example 2 of the present invention, with a magnification of 2000x;
FIG. 6 is a surface electron microscope image of a PES ultrafiltration membrane separation layer provided in example 2 of the present invention, with a magnification of 3000x;
FIG. 7 is a cross-sectional view of the PES ultrafiltration membrane provided in comparative example 3, at 2000X magnification;
FIG. 8 is a cross-sectional view of the PES ultrafiltration membrane provided in comparative example 4, at 2000X magnification.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but it will be understood by those skilled in the art that the following embodiments and examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not specified, and the process is carried out according to conventional conditions or conditions suggested by manufacturers. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the present invention provides a method for preparing a polyethersulfone membrane having a highly asymmetric structure, comprising the steps of:
Coating the casting solution into a liquid film, immersing the liquid film into a coagulating bath for curing to form a film, and washing with water to obtain a polyether sulfone film with a highly asymmetric structure;
The casting solution comprises polyethersulfone, non-solvent and good solvent, wherein the mass proportion of polyethersulfone can be, but is not limited to, 15%, 16%, 17%, 18%, 19% or 20%, and the mass proportion of non-solvent can be, but is not limited to, 40%, 45%, 50%, 55% or 60%;
The non-solvent is at least one of glycerol ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether;
The good solvent comprises at least one of N-N dimethylformamide, N-N dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide;
The coagulating bath comprises a good solvent and water, wherein the mass ratio of the good solvent is 10% -70%, for example, but not limited to 10%, 30%, 50% or 70%, and the temperature of the coagulating bath can be, for example, but not limited to 20 ℃, 30 ℃, 40 ℃ or 50 ℃.
In the phase separation process, common organic solvents are easy to be compatible with non-solvents in the coagulating bath to generate transient phase separation, so that polyether sulfone is easier to separate out, and finally a PES porous membrane with a selective separation layer thickness and small pore diameter gradient change is easy to form. The invention adopts specific ether substances as non-solvent, can effectively control the viscosity of the casting film liquid system, simultaneously slows down the speed of non-solvent diffusion in the coagulating bath into a liquid film by coaction with the coagulating bath in the phase separation process, prolongs the phase separation time, and is favorable for forming a loose and porous spongy pore structure.
According to the preparation method provided by the invention, the ultrafiltration membrane with ideal membrane pore size and high asymmetric structure can be obtained under the combined action of the coagulating bath and the casting membrane liquid system by optimizing the composition and the conditions of the coagulating bath.
In some alternative embodiments, the casting solution further comprises a hydrophilic additive.
In some alternative embodiments, the hydrophilic additive includes, but is not limited to, at least one of polyvinylpyrrolidone, polyethylene glycol, chitosan, polyvinyl alcohol, dextran, lithium chloride, or lithium perchlorate, or other hydrophilic additives known to those skilled in the art are employed to increase the hydrophilicity of the filter membrane.
In some alternative embodiments, the hydrophilic additive may be, for example, but not limited to, 1%, 2%, 3%, or 4% by mass of the casting solution.
In some alternative embodiments, a doctor blade is used to apply the liquid film to the carrier.
In some alternative embodiments, the carrier may be, for example, glass, steel plate, or the like.
In some alternative embodiments, the temperature of the environment during the application of the liquid film may be, for example, but not limited to, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, or 25 ℃ and the humidity may be, for example, but not limited to, 40RH%, 50RH%, 60RH%, or 70RH%.
In some alternative embodiments, the liquid film may be immersed in the coagulation bath for a period of time such as, but not limited to, 1min, 2min, 4min, 6min, 8min, or 10min.
In a second aspect, the invention provides a polyether sulfone membrane with a highly asymmetric structure, which is prepared by the preparation method.
The polyethersulfone membrane can be applied to separation and purification of proteins or viruses. For example, smaller pore size membranes may be used for BSA entrapment and larger pore size membranes may be used for separation of virus and protein mixtures, i.e., entrapping virus, permeating protein.
For the entrapment of BSA, a separation layer is preferably used to face the feed liquid, and for the entrapment of virus, a support layer is preferably used to face the feed liquid, so that the porous support layer can filter the polymer in the protein solution in advance, thereby ensuring high transmittance of the protein.
In some alternative embodiments, the polyethersulfone membrane comprises a selective separation layer and a porous support layer;
the thickness of the separation layer is selected to be 200-500 nm;
The thickness of the polyethersulfone film is 100-150 mu m.
In a third aspect, the present invention provides the use of a polyethersulfone membrane of the highly asymmetric structure described above in protein or viral filtration.
The invention is further illustrated by the following specific examples and comparative examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as limiting the invention in any way.
Example 1
18Wt% of PES, 3wt% of polyethylene glycol, 40wt% of propylene glycol monomethyl ether and 39wt% of N-methyl pyrrolidone are mixed, stirred, stood and defoamed at room temperature, and a clear, uniform and stable casting solution is obtained. Pouring the casting solution on a clean glass carrier, scraping the casting solution into a film shape by using a scraper with 300um, immersing the scraped casting film into a coagulating bath with 10wt% of N-methyl pyrrolidone and 90wt% of deionized water by phase inversion, wherein the temperature of the coagulating bath is room temperature, the residence time is 1min, and then transferring the casting film into pure water. After the membrane is automatically removed, the scraped PES ultrafiltration membrane is placed in deionized water for soaking for 12 h, so as to ensure that the residual organic solvent in the membrane pores is completely removed, and then the PES ultrafiltration membrane is obtained after the membrane is placed in glycerol solution for soaking and drying treatment. As shown in fig. 1.
Example 2
15Wt% of PES, 3wt% of chitosan, 60wt% of ethylene glycol monomethyl ether and 22wt% of N-N dimethylacetamide are mixed, stirred, stood and defoamed at room temperature, and a clear, uniform and stable casting solution is obtained. Pouring the casting solution on a clean glass carrier, scraping the casting solution into a film shape by using a scraper with 300um, immersing the scraped casting film into a coagulating bath with the temperature of 35 ℃ and the residence time of 5min and 40wt% of N-N dimethylacetamide and deionized water by immersing phase conversion, and transferring the scraped casting film into pure water. After the membrane is automatically removed, the scraped PES ultrafiltration membrane is placed in deionized water for soaking for 12h, so as to ensure that the residual organic solvent in the membrane pores is completely removed, and then the PES ultrafiltration membrane is obtained after the membrane is placed in glycerol solution for soaking and drying treatment. As shown in fig. 4-6.
Example 3
Mixing 20wt% of PES, 50wt% of glycerol ether and 30wt% of dimethyl sulfoxide, stirring at room temperature, standing, and defoaming to obtain a clear, uniform and stable casting solution. Pouring the casting solution on a clean glass carrier, scraping the casting solution into a film shape by using a scraper with 300um, immersing the scraped casting film into a coagulation bath with the temperature of 50 ℃ and the residence time of 10min and then transferring the scraped casting film into pure water, wherein the concentration of the dimethyl sulfoxide is 70wt% and the concentration of the deionized water is 30 wt%. After the membrane is automatically removed, the scraped PES ultrafiltration membrane is placed in deionized water for soaking for 12 h, so as to ensure that the residual organic solvent in the membrane pores is completely removed, and then the PES ultrafiltration membrane is obtained after the membrane is placed in glycerol solution for soaking and drying treatment.
Example 4
15Wt% of PES, 3wt% of polyvinylpyrrolidone, 60wt% of ethylene glycol monoethyl ether and 22wt% of N-N dimethylformamide are mixed, stirred, stood still and defoamed at room temperature to obtain a clear, uniform and stable casting solution. Pouring the casting solution on a clean glass carrier, scraping the casting solution into a film shape by using a scraper with 300um, immersing the scraped casting film into a coagulating bath with the temperature of 35 ℃ and the residence time of 5min and 40wt% of N-N dimethylacetamide and deionized water by immersing phase conversion, and transferring the scraped casting film into pure water. After the membrane is automatically removed, the scraped PES ultrafiltration membrane is placed in deionized water for soaking for 12 h, so as to ensure that the residual organic solvent in the membrane pores is completely removed, and then the PES ultrafiltration membrane is obtained after the membrane is placed in glycerol solution for soaking and drying treatment.
Example 5
15Wt% of PES, 3wt% of polyvinyl alcohol, 60wt% of diethylene glycol monomethyl ether and 22wt% of N-N dimethylacetamide are mixed, stirred, stood and defoamed at room temperature, and a clear, uniform and stable casting solution is obtained. Pouring the casting solution on a clean glass carrier, scraping the casting solution into a film shape by using a scraper with 300um, immersing the scraped casting film into a coagulating bath with the temperature of 35 ℃ and the residence time of 5min and 40wt% of N-N dimethylacetamide and deionized water by immersing phase conversion, and transferring the scraped casting film into pure water. After the membrane is automatically removed, the scraped PES ultrafiltration membrane is placed in deionized water for soaking for 12 h, so as to ensure that the residual organic solvent in the membrane pores is completely removed, and then the PES ultrafiltration membrane is obtained after the membrane is placed in glycerol solution for soaking and drying treatment.
Example 6
15Wt% of PES, 3wt% of lithium chloride, 60wt% of diethylene glycol monoethyl ether and 22wt% of N-N dimethylacetamide are mixed, stirred, stood and defoamed at room temperature to obtain a clear, uniform and stable casting solution. Pouring the casting solution on a clean glass carrier, scraping the casting solution into a film shape by using a scraper with 300um, immersing the scraped casting film into a coagulating bath with the temperature of 35 ℃ and the residence time of 5min and 40wt% of N-N dimethylacetamide and deionized water by immersing phase conversion, and transferring the scraped casting film into pure water. After the membrane is automatically removed, the scraped PES ultrafiltration membrane is placed in deionized water for soaking for 12 h, so as to ensure that the residual organic solvent in the membrane pores is completely removed, and then the PES ultrafiltration membrane is obtained after the membrane is placed in glycerol solution for soaking and drying treatment.
Comparative example 1
18 Weight percent of PES, 3 weight percent of polyethylene glycol and 79 weight percent of N-methyl pyrrolidone are stirred, stood and defoamed at room temperature to obtain clear, uniform and stable casting solution. Pouring the casting solution on a clean glass carrier, scraping the casting solution into a film shape by using a scraper with 300um, immersing the scraped casting film into a coagulating bath with 10wt% of N-methyl pyrrolidone and 90wt% of deionized water by phase inversion, wherein the temperature of the coagulating bath is room temperature, the residence time is 1min, and then transferring the casting film into a pure water bath. After the membrane is automatically removed, the scraped PES ultrafiltration membrane is placed in deionized water for soaking for 12 h, so as to ensure that the residual organic solvent in the membrane pores is completely removed, and then the PES ultrafiltration membrane is obtained after the membrane is placed in glycerol solution for soaking and drying treatment. As shown in fig. 2. It can be seen that the film prepared exhibits a finger pore structure due to the absence of non-solvent in the casting solution system of this comparative example.
Comparative example 2
18 Weight percent of PES, 3 weight percent of polyethylene glycol, 10 weight percent of propylene glycol monomethyl ether and 69 weight percent of N-methyl pyrrolidone are mixed, stirred, stood and defoamed at room temperature to obtain a clear, uniform and stable casting solution. Pouring the casting solution on a clean glass carrier, scraping the casting solution into a film shape by using a scraper with 300um, immersing the scraped casting film into a coagulating bath with 10wt% of N-methyl pyrrolidone and 90wt% of deionized water by phase inversion, wherein the temperature of the first coagulating bath is room temperature, the residence time is 1min, and then transferring the casting film into a pure water bath. After the membrane is automatically removed, the scraped PES ultrafiltration membrane is placed in deionized water for soaking for 12h, so as to ensure that the residual organic solvent in the membrane pores is completely removed, and then the PES ultrafiltration membrane is obtained after the membrane is placed in glycerol solution for soaking and drying treatment. As shown in fig. 3. It can be seen that the ratio of the sponge-like pore structure in the cross-sectional structure of the film was increased due to the excessively low content of the non-solvent in the casting film liquid system of the present comparative example, but a uniform sponge-like pore structure could not be formed.
Comparative example 3
Dissolving 15wt% of PES, 3wt% of chitosan and 60wt% of ethylene glycol monomethyl ether in 22wt% of N-N dimethylacetamide, stirring at room temperature, standing and defoaming to obtain a clear, uniform and stable casting solution. Pouring the casting film liquid on a clean glass carrier, scraping the casting film liquid into a film shape by using a scraper with 300um, immersing the scraped casting film into a deionized water coagulation bath through immersion phase conversion, immersing the scraped PES ultrafiltration film in the deionized water for 12 h after the film is automatically fallen off, ensuring that the residual organic solvent in the film holes is completely removed, immersing in a glycerol solution, and drying to obtain the PES ultrafiltration film. As shown in fig. 7. The difference between the comparative example and example 2 is mainly that the coagulation bath is water, and when pure water is used as the coagulation bath, an asymmetric spongy pore structure can be prepared, but the dense cortex of the prepared membrane is thick under the condition, so that the permeability of the membrane is low, and meanwhile, the membrane pores are small and easy to intercept IgG proteins, so that the loss of target products is high.
Comparative example 4
The difference from example 2 is that polyethylene glycol is used as the non-solvent. As shown in fig. 8. It can be seen that when PEG is used as the non-solvent, the membrane is prepared with a partial finger-like pore structure in its cross-sectional structure. And the membrane with the finger-shaped pore structure is applied to virus removal filtration, because the presence of macropore defects can leak viruses, thereby effectively removing the viruses.
Test examples
The filters prepared in the above examples and comparative examples were tested separately and the results were as follows:
1g/L BSA retention and IgG protein transmittance measurement:
The ultrafiltration membrane water flux and the membrane-to-protein rejection rate were tested according to the test standard in national standard GB/T32360 2015. The specific steps are that firstly, the completely wetted film sample is placed in a tangential flow testing device, the film sample is pre-pressed for 30 min under the pressure of 0.15 MPa, then the testing pressure is adjusted to 0.10 MPa, the quality change of pure water penetrating through an ultrafiltration membrane is recorded under the pressure, and the testing process lasts for 30 min. The rejection of BSA by the membrane was measured at 0.1 MPa using 1 g/L BSA solution as feed solution, and the concentration of BSA was measured by uv spectrophotometer. In addition, igG tests can also be performed as described above for standard curve determination and corresponding concentration tests.
Virus retention test:
The method for measuring the virus retention rate can refer to a patent CN 1759924B-ultrafiltration membrane and a preparation method thereof, and a CN 112074340-porous hollow fiber membrane. The cultured phage PP7 stock solution was diluted to a concentration of about 4.0X10 6 PFU/mL as a virus feed solution, and the diluted solution was phosphate buffer solution. Here, the phosphate buffer is a solution after sterilization of 20min using high-pressure steam at 121 ℃. The entrapment test is performed at room temperature with a certain pressure (e.g., 0.2 MPa). The 10mL filtrate collected immediately after filtration was discarded, and then 10mL filtrate was collected again for evaluation of the phage removal rate by the test membrane. Culturing the collected filtrate and virus feed liquid, and comparing plaque formed by phage solution before and after interception on double-layer plate by double-layer plate counting method to evaluate the separation performance of the membrane. Plaque refers to a group of bacteria that infects viruses and dies, and can be counted as punctate plaques. The virus removal performance is expressed by the log virus removal rate (LRV) and the calculation formula is as follows:
LRV=log10[Cfiltrate/Cfeed]。
Wherein, C filtrate is the concentration of virus in the filtrate, and C feed is the concentration of virus in the stock solution.
TABLE 1
。
Note that NA indicates inapplicability.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (10)
1. The preparation method of the polyether sulfone membrane with the highly asymmetric structure is characterized by comprising the following steps of:
Coating the casting solution into a liquid film, immersing the liquid film into a coagulating bath for curing to form a film, and washing with water to obtain a polyether sulfone film with a highly asymmetric structure;
The film casting solution comprises, by mass, 15% -20% of polyethersulfone, 40% -60% of a non-solvent and the balance of a good solvent;
The non-solvent is at least one of glycerol ether, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether;
the good solvent comprises at least one of N-N dimethylformamide, N-N dimethylacetamide, N-methylpyrrolidone or dimethyl sulfoxide;
the coagulating bath comprises a good solvent and water, wherein the mass ratio of the good solvent is 10% -70%, and the temperature of the coagulating bath is 20-50 ℃.
2. The method of claim 1, wherein the casting solution further comprises a hydrophilic additive.
3. The method of claim 2, wherein the hydrophilic additive comprises at least one of polyvinylpyrrolidone, polyethylene glycol, chitosan, polyvinyl alcohol, dextran, lithium chloride, or lithium perchlorate.
4. The method according to claim 2, wherein the hydrophilic additive is present in the casting solution in an amount of 4% by mass or less.
5. The method of claim 1, wherein the liquid film is applied to the support using a doctor blade.
6. The preparation method according to claim 1, wherein the temperature of the environment is 20-25 ℃ and the humidity is 40-70 RH% during the liquid film coating process.
7. The preparation method according to claim 1, wherein the liquid film is immersed in the coagulation bath for 1 to 10 minutes.
8. A polyethersulfone membrane of highly asymmetric structure, characterized in that it is prepared by the preparation method of any one of claims 1 to 7.
9. The highly asymmetric structured polyethersulfone membrane of claim 8, wherein the polyethersulfone membrane comprises a selective separation layer and a porous support layer;
the thickness of the separation layer is selected to be 200-500 nm;
The thickness of the polyethersulfone film is 100-150 mu m.
10. Use of a polyethersulfone membrane of highly asymmetric structure according to claim 8 or 9 for protein or virus filtration.
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