CN109847587A - Low molecular weight retains ultrafiltration membrane and preparation method thereof - Google Patents
Low molecular weight retains ultrafiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses casting solutions, low molecular weight retention ultrafiltration membrane and preparation method thereof.The casting solution includes: 15 parts by weight of polyether sulfone~30 parts by weight, 1 parts by weight of sulfonated polysulfone~4 parts by weight and solvent 46 parts by weight~82.5 parts by weight.The casting solution can prepare ultrafiltration membrane, and the water flux of the ultrafiltration membrane significantly improves, and significantly improve to the rejection performance of small-molecule substance, and the water flux of the ultrafiltration membrane and cutoff performance is made to have reached stable balance in higher level.
Description
Technical field
The present invention relates to membrane preparation method technical fields, in particular it relates to casting solution, ultrafiltration membrane and its preparation side
Method, more particularly it relates to water treatment field and the low molecular weight in feed separation field retention ultrafiltration membrane and its preparation
Method.
Background technique
Membrane separation technique refers to the selected area update strategy effect by film, to mixing under the promotion of outside energy or chemical potential difference
The method that solute and solvent are separated, be classified, purified and be enriched in object.Compared with other traditional separation methods, UF membrane
Have many advantages, such as simple process, better economy, there is no phase transformation, separation larger, energy saving, efficient, without secondary pollution.Film point
Four kinds of reverse osmosis (RO), nanofiltration (NF), ultrafiltration (UF), micro-filtration (MF) isolation technics are broadly divided into from technology, in these four film skills
In art, since the pressure that ultrafiltration uses is low, water yield is larger, therefore is more convenient to operate, and is widely used in water process, health care industry
With food industry etc., development speed quickly, has a extensive future.
There are many polymeric ultrafiltration membranes type being commercialized studied both at home and abroad, the preparation method of polymer-type ultrafiltration membrane
Have very much.Currently, phase inversion has become the mainstream preparation method for preparing polymer film.So-called phase inversion film, exactly makes
The homogeneous polymer solution of standby definite composition changes the thermodynamic state of solution by certain physical method, makes it from homogeneous
Polymer solution separate, be finally converted into the gel structure of a three-dimensional macromolecular network type.
Meanwhile film properties are also constantly improved, according to different application field and environment, different producer's production
Ultrafiltration retaining molecular weight difference is bigger, but the country, which is engaged in ultrafiltration membrane manufacturer, mainly produces molecular cut off 30,000-
150000 ultrafiltration membrane, the ultrafiltration membrane product with low catching molecular (MWCO≤10000Da) is simultaneously few, thus low retention molecule
The ultrafiltration membrane product of amount (MWCO≤10000Da) relies primarily on import at present.
With the development of medical industry and environmental protection industry, in the market to the demand day of low catching molecular ultrafiltration membrane
Benefit increases, therefore, study it is a kind of it is high-throughput, the ultrafiltration membrane of low catching molecular is especially urgent.
Summary of the invention
The application is to be made based on inventor to the discovery of following facts and problem and understanding:
Currently, having carried out many researchs, for membrane material, polyether sulfone to low molecular weight retention ultrafiltration membrane both at home and abroad
It is the membrane material for being now widely used in preparation small-bore ultrafiltration membrane, which has excellent mechanical performance, and good chemistry is steady
Qualitative and thermal stability is easy to form a film, therefore has attracted much attention.But the polymer material has more hydrophobicity due to itself
Group, therefore the polymer material is formed by that film hydrophily is poor, and then the poly (ether sulfone) film pure water flux prepared is very low, Er Qiekang
Pollution capacity is poor, limits its many application.
Based on inventor to above-mentioned true and problem discovery and understanding, the low of the new high throughput of one kind is inventors herein proposed
Molecular weight retain ultrafiltration membrane, the ultrafiltration membrane have good hydrophilic property, resistance tocrocking is strong, water flux is big, to molecular weight less than 10000
The advantage that substance rejection is high, separating property is good, and the ultrafiltration membrane is easy to industrialized production, it is at low cost.
In the first aspect of the present invention, the invention proposes a kind of casting solutions.According to an embodiment of the invention, the casting film
Liquid includes: 15 parts by weight of polyether sulfone~30 parts by weight, and 46 parts by weight of 1 parts by weight of sulfonated polysulfone~4 parts by weight and solvent~
82.5 parts by weight.Casting solution according to an embodiment of the present invention can prepare ultrafiltration membrane, and the water flux of the ultrafiltration membrane significantly improves,
The rejection performance of small-molecule substance is significantly improved, and make ultrafiltration membrane obtained water flux and cutoff performance compared with
Stable balance is reached in high level.
Inventor has found following problem during researching and developing the casting solution of the application and preparing ultrafiltration membrane:
(1) if applying pure polyether sulfone, the ultrafiltration membrane obtained using the casting solution in the formula of casting solution
Water flux and cutoff performance be difficult to reach balance in higher level, and introducing has the sulfonation of hydrophilic sulfonation group poly-
After sulfone, then chemically configuration aspects the hydrophilicity of the ultrafiltration membrane finally obtained can be effectively improved, improve the water of ultrafiltration membrane
Flux；
(2) since polyether sulfone hydrophily itself is not strong, hydrophobic solutes easily block ultrafiltration membrane surface, block fenestra, cause
Fouling membrane leads to the performance sharp fall of film, reduces the service life of ultrafiltration membrane, and introducing has hydrophilic sulfonation group
Sulfonated polysulfone, can reduce the hydrophobicity of polyether sulfone materials, reduce absorption of the hydrophobic substance on film surface, and then reduce film to micro-
The organism of biological bacterium etc. it is affine, and then dramatically increase the resistance tocrocking of ultrafiltration membrane；
(3) there is compared with the polyether sulfone of main body lesser molecular structure, the molecular weight of sulfonated polysulfone due to sulfonated polysulfone
For 30000-60000 dalton, the molecular weight of polyether sulfone turns between 60000-100000 dalton, thus in immersion precipitation phase
When change method forms perforated membrane, sulfonated polysulfone is easier to form the lesser hole in aperture, and after sulfonated polysulfone introduces, it can be in physics knot
The ultrafiltration membrane that finally obtains is improved in terms of structure to the cutoff performance of filtrate, and then improves ultrafiltration membrane to the substance of low molecular weight
Rejection；
(4) if the dosage of sulfonated polysulfone is excessively high, beyond amount ranges of the invention, then the aperture mistake of ultrafiltration membrane is formed
It is small, a relatively compact thin layer can be formed on the ultrafiltration membrane surface layer finally obtained, seriously affect the permeability of the water of ultrafiltration membrane
Can, or even the phenomenon that water flux is zero in the pressure use scope of ultrafiltration membrane is appeared in, additionally, due to sulfonated polysulfone material
Synthesize that difficulty is big, causing the cost of raw material is nearly ten times of the material of main parts such as polyether sulfone or polysulfones, is added beyond the present invention
Sulfonated polysulfone in amount ranges will also result in serious waste；If the dosage of sulfonated polysulfone is too low, lower than use of the invention
Range is measured, then is difficult to obtain the present invention addition sulfonated polysulfone beneficial effect to be obtained.
Based on inventor to the discovery of the above problem in R&D process, inventor takes corresponding solution, obtains
The casting solution of the application.The ultrafiltration membrane prepared using casting solution according to an embodiment of the present invention, is overcome and is surpassed in the prior art
The defect that filter membrane water flux is low, antifouling property is poor realizes ultrafiltration membrane flux height, to the rejection performance of small-molecule substance
Advantage high, antifouling property is high.
According to an embodiment of the invention, above-mentioned casting solution can further include following additional technical feature at least it
One:
According to an embodiment of the invention, the sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-
0.80dL/g.Inventors have found that it is existing that swelling can occur in water for sulfonated polysulfone when the sulfonation degree of sulfonated polysulfone is more than 30%
As in the film forming procedure with immersion precipitation phase inversion process, sulfonated polysulfone will form extremely loose shape structure, cause polyether sulfone
It is poor that the ultrafiltration membrane film-strength to be formed is prepared with the mixing material of sulfonated polysulfone, more difficult can form effective film layer；It is low in sulfonation degree
It is when 10%, then more difficult to obtain mentioned-above beneficial effect, and in the preparation process of casting solution, it is lower than 10% sulfonation degree
Dissolubility of the sulfonated polysulfone in polar organic solvent such as DMAC it is low, be easy to appear solution muddiness solute precipitation phenomenon, cause
Keep addition application more difficult.
According to an embodiment of the invention, the casting solution further comprises: hydrophilic additive.Inventors have found that hydrophilic add
The addition for adding agent is conducive to finally formed ultrafiltration membrane flux and cutoff performance and has reached stable flat in higher level
Weighing apparatus.
According to an embodiment of the invention, the dosage of the hydrophilic additive is 1 parts by weight~15 parts by weight.Invention human hair
Existing, when the dosage of hydrophilic additive is more than 15 parts by weight, the ultrafiltration membrane flux finally obtained is high, but rejection is low, works as parent
When the dosage of aqueous additive is lower than 1 parts by weight, the ultrafiltration membrane flux finally obtained is then relatively very low, in turn, adds when hydrophilic
Add the dosage of agent in 1 parts by weight~15 parts by weight, the water flux and cutoff performance for being more advantageous to the ultrafiltration membrane finally obtained exist
Stable balance is reached in higher level.
According to an embodiment of the invention, the hydrophilic additive includes being selected from polyvinylpyrrolidone, polyethylene glycol, tetrahydro
At least one of furans, sodium chloride, aluminium chloride, sodium sulphate and lithium chloride.
According to an embodiment of the invention, the hydrophilic additive is polyethylene glycol.
According to an embodiment of the invention, the molecular weight of the polyethylene glycol is less than 2000.Inventors have found that polyethylene glycol
Molecular weight is conducive to ultrafiltration membrane surface layer and forms small aperture, the substance to low molecular weight less than 10000 dalton has less than 2000
High cutoff performance, separating property.
According to an embodiment of the invention, the casting solution further comprises: non-solvent.Be conducive to polyether sulfone, sulfonation as a result,
The dissolution of polysulfones with mix.
According to an embodiment of the invention, the dosage of the non-solvent is 0.5 parts by weight~5 parts by weight.Inventors have found that non-
The dosage of solvent is more than 5 parts by weight, is unfavorable for the dissolution and mixing of polyether sulfone and sulfonated polysulfone, is unfavorable for forming a film, film makes
It is poor with performance；When the dosage of non-solvent is lower than 0.5 parts by weight, the then finger-hole of connectivity difference easy to form, finally formed ultrafiltration
The water flux of film is relatively low.
According to an embodiment of the invention, the non-solvent include selected from water, citric acid, acetic acid and phosphoric acid at least it
One.Be conducive to as a result, polyether sulfone, sulfonated polysulfone dissolution with mix.
According to an embodiment of the invention, the non-solvent is water.It is more advantageous to the dissolution of polyether sulfone, sulfonated polysulfone as a result,
With mix.
According to an embodiment of the invention, the solvent includes being selected from dimethylformamide, dimethyl acetamide, N- methyl pyrrole
At least one of pyrrolidone, dimethyl sulfoxide and triethyl phosphate.Be conducive to as a result, polyether sulfone, sulfonated polysulfone dissolution with
Mixing.
In the second aspect of the present invention, the invention proposes a kind of casting solutions.According to an embodiment of the invention, the casting film
Liquid includes: 15 parts by weight of polyether sulfone~30 parts by weight, 1 parts by weight of sulfonated polysulfone~4 parts by weight, 1 parts by weight~15 of polyethylene glycol
Parts by weight, 0.5 parts by weight of water~5 parts by weight and balance solvent, wherein the solvent be include selected from dimethylformamide,
At least one of dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and triethyl phosphate, the polyethylene glycol
For molecular weight less than 2000, the sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-0.80dL/g.Inventor
It was found that sulfonation degree 10%-30%, intrinsic viscosity 0.65-0.80dL/g, 1 parts by weight of dosage~4 parts by weight sulfonated polysulfone
Introducing improve the hydrophilicity of the ultrafiltration membrane finally obtained chemically in the angle of structure and physical structure, reduce super
The hydrophobicity of filter membrane film, to improve the resistance tocrocking of ultrafiltration membrane；In addition molecular weight less than 2000 polyethylene glycol with it is non-molten
The mixing application of agent water is then easy to produce the finger aperture arrangement of perforation and the mixing of surface layer aperture in the preparation process of ultrafiltration membrane
The cutoff performance to substance is greatly improved while guaranteeing high water flux in structure, especially to small-molecule substance,
The rejection performance of substance of the molecular weight less than 10000, so that both the water flux of the ultrafiltration membrane finally obtained and rejection exist
Stable balance is reached in higher level.Have as a result, using the ultrafiltration membrane that the casting solution of the embodiment of the present invention obtains steady
Qualitative advantage good, resistance tocrocking is good, water flux is big and substance rejection to molecular weight less than 10000 is high.
In the third aspect of the present invention, the invention proposes a kind of ultrafiltration membranes.According to an embodiment of the invention, the ultrafiltration
Film is obtained by the way that mentioned-above casting solution is carried out blade coating film process.According to an embodiment of the invention, described " scrapes
Painting film process ", which refer to, is coated uniformly on braided fabric or other template surfaces formation nascent state for casting solution using knife type coater
Film later again evaporates nascent state film the regular hour in air bath, and inversion of phases film process are then carried out in coagulating bath,
To obtain ultrafiltration membrane.Ultrafiltration membrane according to an embodiment of the present invention shows apparent finger-like pore unsymmetric structure, has and stablizes
Property it is good, resistance tocrocking is good, water flux is big, the substance rejection to molecular weight less than 10000 is high, advantage at low cost, can apply
In clean water treatment, wastewater treatment, the fields such as feed separation.
In the fourth aspect of the present invention, the invention proposes a kind of ultrafiltration membranes.According to an embodiment of the invention, the polyethers
15 parts by weight of sulfone~30 parts by weight, 1 parts by weight of sulfonated polysulfone~4 parts by weight and solvent 46 parts by weight~82.5 parts by weight.Root
Apparent finger-like pore unsymmetric structure is showed according to the ultrafiltration membrane of the embodiment of the present invention, with stability is good, resistance tocrocking is good, water
The big substance rejection to molecular weight less than 10000 of flux is high, advantage at low cost, can be applied to clean water treatment, at waste water
Reason, the fields such as feed separation.
According to an embodiment of the invention, above-mentioned ultrafiltration membrane can further include following additional technical feature at least it
One:
According to an embodiment of the invention, the sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-
0.80dL/g.Inventors have found that it is existing that swelling can occur in water for sulfonated polysulfone when the sulfonation degree of sulfonated polysulfone is more than 30%
As in the film forming procedure with immersion precipitation phase inversion process, sulfonated polysulfone will form extremely loose shape structure, cause polyether sulfone
The intensity difference for the ultrafiltration membrane to be formed is prepared with the mixing material of sulfonated polysulfone, more difficult can form effective film layer；It is low in sulfonation degree
It is when 10%, then more difficult to obtain mentioned-above beneficial effect, and in the preparation process of casting solution, it is lower than 10% sulfonation degree
Dissolubility of the sulfonated polysulfone in polar organic solvent such as dimethyl acetamide (DMAC) it is low, it is molten to be easy to appear solution muddiness
Matter precipitation phenomenon causes addition application more difficult.
According to an embodiment of the invention, the ultrafiltration membrane further comprises: hydrophilic additive.Inventors have found that hydrophilic add
The addition for adding agent, the water flux and cutoff performance for being conducive to ultrafiltration membrane have reached stable balance in higher level.
According to an embodiment of the invention, the dosage of the hydrophilic additive is 1 parts by weight~15 parts by weight.Invention human hair
Existing, when the dosage of hydrophilic additive is more than 15 parts by weight, the ultrafiltration membrane flux finally obtained is high, but rejection is low, works as parent
When the dosage of aqueous additive is lower than 1 parts by weight, the ultrafiltration membrane flux finally obtained is then relatively very low, in turn, adds when hydrophilic
Add the dosage of agent in 1 parts by weight~15 parts by weight, the water flux and cutoff performance for being more advantageous to ultrafiltration membrane are in higher level
On reached stable balance.
According to an embodiment of the invention, the hydrophilic additive is polyethylene glycol.
According to an embodiment of the invention, the molecular weight of the polyethylene glycol is less than 2000.Inventors have found that polyethylene glycol
Molecular weight is conducive to ultrafiltration membrane surface layer and forms small aperture, the substance to low molecular weight less than 10000 dalton has less than 2000
High cutoff performance, separating property.
In the fourth aspect of the present invention, the invention proposes a kind of methods for preparing ultrafiltration membrane.Implementation according to the present invention
Example, which comprises mixed processing is carried out to polyether sulfone, sulfonated polysulfone, solvent；Gained mixed liquor is carried out at standing and defoaming
Reason；And treated that mixed liquor carries out blade coating film process by standing and defoaming, to obtain ultrafiltration membrane；Wherein, the polyethers
Sulfone, sulfonated polysulfone, solvent amount ratio be (15~30) g:(1~4) g:(46~82.5) g.As previously mentioned, real according to the present invention
The method for applying example is simple, at low cost, and it is non-that the ultrafiltration membrane obtained according to the method for the embodiment of the present invention shows apparent finger-like pore
Symmetrical structure, have stability is good, resistance tocrocking is good, water flux is big, the substance rejection height to molecular weight less than 10000, at
This low advantage can be applied to water process, wastewater treatment, the fields such as feed separation.
According to an embodiment of the invention, the above method can further include at least one following additional technical feature:
According to an embodiment of the invention, the sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-
0.80dL/g.Inventors have found that it is existing that swelling can occur in water for sulfonated polysulfone when the sulfonation degree of sulfonated polysulfone is more than 30%
As in the film forming procedure with immersion precipitation phase inversion process, sulfonated polysulfone will form extremely loose shape structure, cause polyether sulfone
The intensity difference for the ultrafiltration membrane to be formed is prepared with the mixing material of sulfonated polysulfone, more difficult can form effective film layer；It is low in sulfonation degree
It is when 10%, then more difficult to obtain mentioned-above beneficial effect, and in the preparation process of casting solution, it is lower than 10% sulfonation degree
Dissolubility of the sulfonated polysulfone in polar organic solvent such as DMAC it is low, be easy to appear solution muddiness solute precipitation phenomenon, cause
Keep addition application more difficult.
According to an embodiment of the invention, the blade coating film process include that the mixed liquor is coated in braided fabric or template
Surface, and the mixed liquor for being coated in braided fabric or template surface is subjected to striking, evaporation, solidification processing.It should be noted that scraping
After system processing, before evaporation process, mixed liquor can be described as nascent state film in the film that braided fabric or template surface are formed.
According to an embodiment of the invention, the blade coating with a thickness of 80-120 μm.Applying material according to the present invention is consolidated
Body content, thickness of dry film is at 45-55 μm, if scraping film thickness is more than 120 microns, the thickness of dry film of ultrafiltration membrane is partially thick, film
Water flux performance is relatively low, if scraping film thickness lower than 80 microns, the thickness of dry film of ultrafiltration membrane is partially thin, and the cutoff performance of film is inclined
It is low, or even will appear the phenomenon that can not forming a film.
According to an embodiment of the invention, the evaporation process is to carry out 10 under the conditions of temperature is 12-28 DEG C of air bath
~20s.Inventors have found that the evaporation process that 10~20s is carried out under conditions of air bath, which is conducive to nascent state film, becomes fine and close,
The exchange rate that water and solvent in solidification processing can be reduced, reduces the formation of macropore, improves the rejection of ultrafiltration membrane.Air
The time of bath evaporation is shorter than 10s, then the rejection of the ultrafiltration membrane prepared according to the method for the embodiment of the present invention is relatively low；Air
The time of bath evaporation is longer than 20s, then nascent state film becomes excessively fine and close, and water flux is lower, and be relatively inaccessible to using requirement.This
Field technical staff will be understood by, and the time of air bath is very short, and solvent evaporation amount is few, can be neglected.
According to an embodiment of the invention, the solidification processing is carried out by coagulating bath, the temperature of the coagulating bath is 5
~60 DEG C.Inventors have found that the temperature of coagulating bath is 5~60 DEG C of porosity and holes for being conducive to adjust the ultrafiltration membrane finally obtained
Structure can obtain flux and the higher ultrafiltration membrane of rejection.
According to an embodiment of the invention, the coagulating bath is water-bath, or the water-bath containing organic solvent is described organic
Solvent includes being selected from dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, propyl alcohol, dehydrated alcohol
And at least one of ethylene glycol.Inventors have found that water-bath, or the water-bath containing organic solvent are conducive to keep solidification
The temperature of bath, and each position of nascent state film is cooled uniformly.
According to an embodiment of the invention, the polyether sulfone, sulfonated polysulfone are previously dried processing.
According to an embodiment of the invention, it is described drying process be temperature be 40 DEG C~100 DEG C under conditions of carry out 2~
6h。
According to an embodiment of the invention, the mixed processing carries out in the following way: a) gathering polyether sulfone, sulfonation
Sulfone, solvent stir immersion 1~2 hour, b under the conditions of 25 DEG C) mixed liquor after stirring is impregnated in step a) is carried out at dissolution
Reason, the dissolution process are to be 50~80 DEG C in temperature to carry out 5~6 hours.
According to an embodiment of the invention, standing and defoaming processing be carry out 4 under conditions of temperature is 25~80 DEG C~
8h。
According to an embodiment of the invention, the solvent includes being selected from dimethylformamide, dimethyl acetamide, N- methyl pyrrole
At least one of pyrrolidone, dimethyl sulfoxide and triethyl phosphate.Be conducive to as a result, polyether sulfone, sulfonated polysulfone dissolution with
Mixing.
According to an embodiment of the invention, the mixed processing further comprises gathering hydrophilic additive, non-solvent with described
Ether sulfone, sulfonated polysulfone, solvent carry out mixed processing.
According to an embodiment of the invention, the amount ratio of the polyether sulfone, sulfonated polysulfone, solvent, hydrophilic additive be (15~
30): (1~4): (46~82.5): (1~15).Inventors have found that the dosage when hydrophilic additive is higher than amount ratio of the invention
Range, the ultrafiltration membrane flux finally obtained is high, but rejection is low, when the dosage of hydrophilic additive is lower than dosage of the invention
Than range, the ultrafiltration membrane flux finally obtained is then relatively very low, in turn, when the dosage of hydrophilic additive is in dosage of the invention
Than range, the water flux and cutoff performance for being more advantageous to the ultrafiltration membrane obtained according to the method for the embodiment of the present invention are in higher water
Stable balance is reached on flat.
According to an embodiment of the invention, the hydrophilic additive includes being selected from polyvinylpyrrolidone, polyethylene glycol, tetrahydro
At least one of furans, sodium chloride, aluminium chloride, sodium sulphate and lithium chloride.
According to an embodiment of the invention, the hydrophilic additive is polyethylene glycol.
According to an embodiment of the invention, the molecular weight of the polyethylene glycol is less than 2000.Inventors have found that polyethylene glycol
Molecular weight is conducive to ultrafiltration membrane surface layer and forms small aperture, the substance to low molecular weight less than 10000 dalton has less than 2000
High cutoff performance, separating property.
According to an embodiment of the invention, the amount ratio of the polyether sulfone, sulfonated polysulfone, solvent, hydrophilic additive, non-solvent
For (15~30) g:(1~4) g:(46~82.5) g:(1~15) g:(0.5~5) g.Inventors have found that the dosage of non-solvent is high
In amount ratio range of the invention, it is unfavorable for the dissolution and mixing of polyether sulfone and sulfonated polysulfone, is unfavorable for forming a film, the use of film
Performance is poor；When the dosage of non-solvent is lower than amount ratio range of the invention, then the finger-hole of connectivity difference easy to form, ultimately forms
Ultrafiltration membrane water flux it is relatively low.
According to an embodiment of the invention, the non-solvent include selected from water, citric acid, acetic acid and phosphoric acid at least it
One.Be conducive to as a result, polyether sulfone, sulfonated polysulfone dissolution with mix.
According to an embodiment of the invention, the non-solvent is water.It is more advantageous to the dissolution of polyether sulfone, sulfonated polysulfone as a result,
With mix.
In the fifth aspect of the invention, the invention proposes a kind of methods for preparing ultrafiltration membrane.Implementation according to the present invention
Example, which comprises 1) polyether sulfone, sulfonated polysulfone, solvent, polyethylene glycol, water are stirred to immersion 1~2 under the conditions of 25 DEG C
Hour, the polyether sulfone, sulfonated polysulfone are previously dried processing, and the drying process is the item for being 40~100 DEG C in temperature
2~6h is carried out under part；2) mixed liquor after impregnating stirring in step 1) carries out dissolution process, and the dissolution process is in temperature
It is carried out 5~6 hours for 50~80 DEG C；3) mixed liquor after dissolution process in step 2) is subjected to standing and defoaming processing, the standing
Deaeration processing be temperature be 25~80 DEG C under conditions of carry out 4~8h, 4) by standing and defoaming in step 3) treated mixing
Liquid carries out blade coating film process, and to obtain ultrafiltration membrane, the blade coating film process include that the mixed liquor is coated in braiding
Object or template surface, and the mixed liquor for being coated in braided fabric or template surface is subjected to striking, evaporation, solidification processing, it is described to scrape
Apply with a thickness of 80-120 μm, the evaporation process is that 10~20s, institute are carried out under the conditions of temperature is 12-28 DEG C of air bath
Stating solidification processing is carried out by coagulating bath, and the temperature of the coagulating bath is 5~60 DEG C, and the coagulating bath is water-bath, or
It is the water-bath containing organic solvent, the organic solvent includes being selected from dimethylformamide, dimethyl acetamide, N- methylpyrrole
At least one of alkanone, dimethyl sulfoxide, propyl alcohol, dehydrated alcohol and ethylene glycol, wherein the polyether sulfone, sulfonated polysulfone,
Solvent, hydrophilic additive, non-solvent amount ratio be (15~30): (1~4): (46~82.5): (1~15): (0.5~5),
The sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-0.80dL/g；The solvent includes being selected from diformazan
At least one of base formamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and triethyl phosphate；It is described
The molecular weight of polyethylene glycol is less than 2000.As previously mentioned, it is simple according to the method for the embodiment of the present invention, it is at low cost, according to this hair
The ultrafiltration membrane that the method for bright embodiment obtains shows apparent finger-like pore unsymmetric structure, the good, resistance tocrocking with stability
Well, the big substance rejection height to molecular weight less than 10000 of water flux, advantage at low cost, can be applied to water process, waste water
Processing, the fields such as feed separation.
Specific embodiment
The embodiment of the present invention is described below in detail.The following examples are exemplary, it is intended to it is used to explain the present invention,
And it is not considered as limiting the invention.
The water flux test method of ultrafiltration membrane is in the embodiment of the present invention: ultrafiltration membrane being fitted into membrane cisterna, 0.35MPa's
It is 0.2MPa in pressure under pressure after precompressed 0.5 hour, temperature measures 1 hour water transit dose Q under conditions of being 25 DEG C, and
It is calculated by the following formula to obtain water flux J:
J=Q/ (St)
J: water flux, unit are L/m2h；
Q: water transit dose, unit are L；
S: diaphragm area, unit are m2；
T: time, unit are h.
Ultrafiltration membrane is to the rejection test method of different molecular weight in the embodiment of the present invention: ultrafiltration membrane is packed into membrane cisterna
In, it is 0.2MPa in pressure, temperature tests different points under conditions of being 25 DEG C under the pressure of 0.35MPa after precompressed 0.5 hour
The Aqueous Solutions of Polyethylene Glycol original liquid concentration of son amount is calculated by the following formula by the concentration of polyethylene glycol in test permeate
Obtain rejection:
R=(Cp-Cf)/Cp× 100%
R: rejection, unit are %；
Cp: the concentration of polyethylene glycol in raw water, unit are mg/L；
Cf: the concentration of polyethylene glycol in permeate, unit are mg/L.
Embodiment 1
62g dimethyl acetamide is added in 250mL three-necked flask, 8g polyethylene glycol-800, the non-solvent of 1g is added
Water is sufficiently mixed uniformly, adds polyether sulfone 25g, sulfonation degree 10%, intrinsic viscosity 0.80dL/g, and molecular weight is
The sodium form sulfonated polysulfone 4g of 30000-60000 dalton is stirred immersion 1 hour at room temperature, is then heated to 60 DEG C of dissolutions 6
Hour, being made into total polymer concentration is 29wt%, and wherein sulfonated polysulfone concentration is 4wt%, and hydrophilic additive concentration is 8wt%,
The concentration of non-solvent is 1wt%, and surplus is the casting solution of solvent, standing and defoaming 8h under the conditions of 60 DEG C are enclosed in after filtering.
Then the complete casting solution of deaeration is cast on polyester non-woven fabric in clean casting film room, with stainless steel spatula
Striking film forming, air evaporation 20s are put into rapidly in the solidification water-bath that temperature is 25 DEG C, take out after 24 hours to be solidified, use water
Sufficiently it is stored in after cleaning in protection liquid to get ultrafiltration membrane.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 156.4L/ (m2It h), is 95.6% to PEG10000 (relative molecular mass 10000) rejection.
Embodiment 2
The preparation condition of casting solution is with embodiment 1, and using 62g dimethylformamide, 8g polyethylene glycol 2000,1g's is non-molten
Agent water, polyether sulfone 25g, sulfonation degree 30%, intrinsic viscosity 0.65dL/g, molecular weight are the sodium of 30000-60000 dalton
Type sulfonated polysulfone 4g, be stirred at room temperature immersion 1 hour, after be heated to 60 DEG C dissolve 6 hours, being made into total polymer concentration is
29wt%, wherein sulfonated polysulfone concentration is 4wt%, and hydrophilic additive concentration is 8wt%, and the concentration of non-solvent is 1wt%, surplus
For the casting solution of solvent, standing and defoaming 8h under the conditions of 60 DEG C are enclosed in after filtering.
The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 161.9/ (m2It h), is 93.7% to PEG10000 (relative molecular mass 10000) rejection.
Embodiment 3
The preparation condition of casting solution is with embodiment 1, and using 65g N-Methyl pyrrolidone, 8g polyethylene glycol-800,1g's is non-
Aqueous solvent, polyether sulfone 25g, sulfonation degree 20%, intrinsic viscosity 0.70dL/g, molecular weight are 30000-60000 dalton
Sodium form sulfonated polysulfone 1g, be stirred at room temperature immersion 1 hour, after be heated to 60 DEG C dissolve 6 hours, be made into total polymer concentration
For 26wt%, wherein sulfonated polysulfone concentration is 1wt%, and hydrophilic additive concentration is 8wt%, and the concentration of non-solvent is 1wt%, remaining
Amount is the casting solution of solvent, standing and defoaming 8h under the conditions of 60 DEG C are enclosed in after filtering.The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 165.3L/ (m2It h), is 93.2% to PEG10000 (relative molecular mass 10000) rejection.
Embodiment 4
The preparation condition of casting solution is with embodiment 1, and using 61g dimethyl acetamide, 15g polyethylene glycol 400,5g's is non-molten
Agent water, polyether sulfone 15g, sulfonation degree 10%, intrinsic viscosity 0.80dL/g, molecular weight are the sodium of 30000-60000 dalton
Type sulfonated polysulfone 4g, be stirred at room temperature immersion 1 hour, after be heated to 60 DEG C dissolve 6 hours, being made into total polymer concentration is
19wt%, wherein sulfonated polysulfone concentration is 4wt%, and hydrophilic additive concentration is 15wt%, and the concentration of non-solvent is 5wt%, remaining
Amount is the casting solution of solvent, standing and defoaming 8h under the conditions of 60 DEG C are enclosed in after filtering.The preparation condition of film is the same as embodiment 1.
The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 168.7.2L/ (m2It h), is 92.1% to PEG10000 (relative molecular mass 10000) rejection.
Comparative example 1 (is added without sulfonated polysulfone)
The preparation condition of casting solution is with embodiment 1, using 66g dimethyl acetamide, 1g non-solvent water, 8g polyethylene glycol
Sodium form sulfonated polysulfone is not added by 800, polyether sulfone 25g, and being configured to total polymer concentration is 25wt%, and hydrophilic additive concentration is
8wt%, the concentration of non-solvent are 1wt%, remaining is the formula of casting of solvent.
The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 147.2L/ (m2It h), is 56.1% to PEG10000 (relative molecular mass 10000) rejection.
(sulfonation degree and intrinsic viscosity of sulfonated polysulfone are not 10%-30% in sulfonation degree to comparative example 2, and intrinsic viscosity is
The range of 0.65-0.80dL/g)
The preparation condition of casting solution is with embodiment 1, using 62g dimethyl acetamide, 1g non-solvent water, 8g polyethylene glycol
800, polyether sulfone 25g, it is 40% that sulfonation degree, which is added, intrinsic viscosity 0.55dL/g, and molecular weight is the sodium form sulphur of 30000-60000
Change polysulfones 4g, being configured to total polymer concentration is 29wt%, and hydrophilic additive concentration is 8wt%, and the concentration of non-solvent is
1wt%, remaining is the formula of casting of solvent.The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 363.5L/ (m2It h), is 16.1% to PEG10000 (relative molecular mass 10000) rejection.
Comparative example 3 (dosage of sulfonated polysulfone is higher than 4 parts by weight)
The preparation condition of casting solution is with embodiment 1, using 56g dimethyl acetamide, 1g non-solvent water, 8g polyethylene glycol
800, polyether sulfone 25g, it is 20% that sulfonation degree, which is added, intrinsic viscosity 0.70dL/g, and molecular weight is the sodium form sulphur of 30000-60000
Change polysulfones 10g, being configured to total polymer concentration is 32wt%, and the dosage of sulfonated polysulfone is 10wt%, the dosage of hydrophilic additive
For 8wt%, the dosage of non-solvent is 1wt%, remaining is the formula of casting of solvent.
The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 65L/ (m2It h), is 96.1% to PEG10000 (relative molecular mass 10000) rejection.
(sulfonation degree and intrinsic viscosity of sulfonated polysulfone are not 10%-30% in sulfonation degree to comparative example 4, and intrinsic viscosity is
In the range of 0.65-0.80dL/g)
The preparation condition of casting solution is with embodiment 1, using 62g dimethyl acetamide, 1g non-solvent water, 8g polyethylene glycol
1000, polyether sulfone 25g, it is 5% that sulfonation degree, which is added, intrinsic viscosity 0.85dL/g, and molecular weight is the sodium form sulphur of 30000-60000
Change polysulfones 4g, being configured to total polymer concentration is 29wt%, and the dosage of sulfonated polysulfone is 4wt%, hydrophilic additive mass concentration
For 8wt%, the dosage of non-solvent is 1wt%, remaining is the formula of casting of solvent.
The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 133.7L/ (m2It h), is 65.1% to PEG10000 (relative molecular mass 10000) rejection.This is because sulfonation is poly-
The sulfonation degree of sulfone is lower than 10%, and intrinsic viscosity is higher than 0.80dL/g, the pure water flux 156.4L/ of water flux and rejection performance
(m2H), and to the rejection of PEG10000 (relative molecular mass 10000) 95.6%, that is, it is not achieved what the present invention was described
Beneficial effect.
(hydrophilic additive is polyethylene glycol to comparative example 5, but molecular weight is beyond 2000)
The preparation condition of casting solution is with embodiment 1, using 62g dimethyl acetamide, 1g non-solvent water, 8g polyethylene glycol
4000, polyether sulfone 25g, it is 20% that sulfonation degree, which is added, intrinsic viscosity 0.70dL/g, and molecular weight is the sodium form of 30000-60000
Sulfonated polysulfone 4g, being configured to total polymer concentration is 29wt%, and the dosage of sulfonated polysulfone is 4wt%, and hydrophilic additive quality is dense
Degree is 8wt%, and the dosage of non-solvent is 1wt%, remaining is the formula of casting of solvent.
The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 145.9L/ (m2It h), is 77.8% to PEG10000 (relative molecular mass 10000) rejection.
Comparative example 6 (hydrophilic additive is polyvinylpyrrolidone)
The preparation condition of casting solution is with embodiment 1, using 62g dimethyl acetamide, 1g non-solvent water, 8g polyvinyl pyrrole
Alkanone, polyether sulfone 25g, it is 20% that sulfonation degree, which is added, intrinsic viscosity 0.70dL/g, and molecular weight is the sodium form of 30000-60000
Sulfonated polysulfone 4g, being configured to total polymer concentration is 29wt%, and the dosage of sulfonated polysulfone is 4wt%, and hydrophilic additive quality is dense
Degree is 8wt%, and the dosage of non-solvent is 1wt%, remaining is the formula of casting of solvent.
The preparation condition of film is the same as embodiment 1.
It is 0.2MPa in pressure, feed liquid temperature is at 25 DEG C, and the pure water of the film is logical according to conventional film properties evaluation method
Amount is 148.9L/ (m2It h), is 47.8% to PEG10000 (relative molecular mass 10000) rejection.
Find out from embodiment 1 and comparative example 1, comparative example 4, comparative example 1 is not added with sulfonated polysulfone, comparative example 4 has used sulphur
Change degree and intrinsic viscosity are not 10%-30% in sulfonation degree, and the sulfonation in the range of intrinsic viscosity is 0.65-0.80dL/g is poly-
Sulfone, it is low to PEG10000 (relative molecular mass 10000) rejection for the ultrafiltration membrane that comparative example 1 and 4 is prepared, and is pressing
Power is 0.2MPa, and feed liquid temperature is at 25 DEG C, and the pure water flux of the film reduces 10%-20%, and rejection reduces nearly
50%.
It is compared from embodiment 1 with comparative example 2, comparative example 2 joined sulfonation degree higher than 30%, and intrinsic viscosity is lower than 0.60
Sulfonated polysulfone causes to form a film loose since the sulfonation degree of sulfonated polysulfone is excessively high, and the mechanical performance of film substantially weakens, thus film
Rejection is extremely low, and there is no use value in practical applications.
It is compared from embodiment 1 with comparative example 3, the dosage that sulfonated polysulfone is added in comparative example 3 is higher than 4 parts by weight, result table
Bright, water flux is greatly reduced, this is because the dosage of sulfonated polysulfone is excessively high, results in fine and close surface layer film, leads to the water of film
Flux performance is extremely low.This is also not no practical value in practical applications.And due to sulfonated polysulfone material, synthetic technology
Difficulty is high, and causing the cost of the raw material is nearly ten times of the material of main parts such as polyether sulfone or polysulfones.Dosage is excessively high, undoubtedly improves
Production cost.Reduce profit.
It is compared from embodiment 1 with comparative example 5, comparative example 6, comparative example 5 joined the polyethylene glycol that molecular weight is greater than 2000
As hydrophilic additive, the hydrophilic additive that comparative example 6 is added is polyvinylpyrrolidone, ultrafiltration membrane prepared by comparative example 5 and 6
Water flux it is preferable, but the ultrafiltration membrane for being not so good as embodiment 1 to the rejection of low molecular weight substance polyethylene glycol 10000 is high.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or spy described in conjunction with this embodiment or example
Point is included at least one embodiment or example of the invention.In the present specification, schematic expression of the above terms are not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It can be combined in any suitable manner in one or more embodiment or examples.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the feature of different embodiments or examples described in this specification and different embodiments or examples
It closes and combines.
Although the embodiments of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is not considered as limiting the invention, those skilled in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, modifies, replacement and variant.
Claims (10)
1. a kind of casting solution characterized by comprising
15 parts by weight of polyether sulfone~30 parts by weight,
1 parts by weight of sulfonated polysulfone~4 parts by weight, and
46 parts by weight of solvent~82.5 parts by weight.
2. casting solution according to claim 1, which is characterized in that the sulfonation degree of the sulfonated polysulfone is 10%-30%, Gu
Having viscosity is 0.65-0.80dL/g.
3. casting solution according to claim 1, which is characterized in that further comprise: hydrophilic additive,
Optionally, the dosage of the hydrophilic additive is 1 parts by weight~15 parts by weight；
Optionally, the hydrophilic additive includes being selected from polyvinylpyrrolidone, polyethylene glycol, tetrahydrofuran, sodium chloride, chlorination
At least one of aluminium, sodium sulphate and lithium chloride；
Preferably, the hydrophilic additive is polyethylene glycol；
Optionally, the molecular weight of the polyethylene glycol is less than 2000.
4. casting solution according to claim 1, which is characterized in that further comprise: non-solvent,
Optionally, the dosage of the non-solvent is 0.5 parts by weight~5 parts by weight；
Optionally, the non-solvent includes selected from least one of water, citric acid, acetic acid and phosphoric acid；
Preferably, the non-solvent is water；
Optionally, the solvent includes sub- selected from dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl
At least one of sulfone and triethyl phosphate.
5. a kind of casting solution, which is characterized in that including
15 parts by weight of polyether sulfone~30 parts by weight,
1 parts by weight of sulfonated polysulfone~4 parts by weight,
1 parts by weight of polyethylene glycol~15 parts by weight,
0.5 parts by weight of water~5 parts by weight, and
Balance solvent,
Wherein, the solvent is to include selected from dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl Asia
At least one of sulfone and triethyl phosphate,
The molecular weight of the polyethylene glycol less than 2000,
The sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-0.80dL/g.
6. a kind of ultrafiltration membrane, which is characterized in that be by scratching into the described in any item casting solutions of Claims 1 to 5
What film process obtained.
7. a kind of ultrafiltration membrane characterized by comprising 15 parts by weight of polyether sulfone~30 parts by weight,
1 parts by weight of sulfonated polysulfone~4 parts by weight, and
46 parts by weight of solvent~82.5 parts by weight；
Preferably, the sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-0.80dL/g；
Optionally, further comprise: hydrophilic additive；
Optionally, the dosage of the hydrophilic additive is 1 parts by weight~15 parts by weight；
Preferably, the hydrophilic additive is polyethylene glycol；
Optionally, the molecular weight of the polyethylene glycol is less than 2000.
8. a kind of method for preparing ultrafiltration membrane, which is characterized in that
Mixed processing is carried out to polyether sulfone, sulfonated polysulfone, solvent；
Gained mixed liquor is subjected to standing and defoaming processing；And
By standing and defoaming, treated that mixed liquor carries out blade coating film process, to obtain ultrafiltration membrane；
Wherein, the polyether sulfone, sulfonated polysulfone, solvent amount ratio be (15~30): (1~4): (46~82.5).
9. according to the method described in claim 8, the sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-
0.80dL/g；
Optionally, the blade coating film process include the mixed liquor being coated in braided fabric or template surface, and will be coated in
The mixed liquor of braided fabric or template surface carries out striking, evaporation, solidification processing；
Optionally, the blade coating with a thickness of 80-120 μm
Optionally, the evaporation process is that 10~20s is carried out under the conditions of temperature is 12-28 DEG C of air bath；
Optionally, the solidification processing is carried out by coagulating bath, and the temperature of the coagulating bath is 5~60 DEG C；
Optionally, the coagulating bath is water-bath, or the water-bath containing organic solvent, and the organic solvent includes being selected from diformazan
In base formamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, propyl alcohol, dehydrated alcohol and ethylene glycol extremely
It is one of few；
Optionally, the polyether sulfone, sulfonated polysulfone are previously dried processing；
Optionally, the drying process is that 2~6h is carried out under conditions of temperature is 40 DEG C~100 DEG C；
Optionally, the mixed processing carries out in the following way:
A) polyether sulfone, sulfonated polysulfone, solvent are stirred to immersion 1~2 hour under the conditions of 25 DEG C,
B) mixed liquor after impregnating stirring in step a) carries out dissolution process, and it is 50~80 DEG C that the dissolution process, which is in temperature,
It carries out 5~6 hours；
Optionally, the standing and defoaming processing is that 4~8h is carried out under conditions of temperature is 25~80 DEG C.
Optionally, the solvent includes sub- selected from dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl
At least one of sulfone and triethyl phosphate；
Optionally, the mixed processing further comprises by hydrophilic additive, non-solvent and the polyether sulfone, sulfonated polysulfone, molten
Agent carries out mixed processing；
Optionally, the polyether sulfone, sulfonated polysulfone, solvent, hydrophilic additive amount ratio be (15~30): (1~4): (46~
82.5): (1~15)；
Optionally, the hydrophilic additive includes being selected from polyvinylpyrrolidone, polyethylene glycol, tetrahydrofuran, sodium chloride, chlorination
At least one of aluminium, sodium sulphate and lithium chloride；
Preferably, the hydrophilic additive is polyethylene glycol；
Optionally, the molecular weight of the polyethylene glycol is less than 2000；
Optionally, the polyether sulfone, sulfonated polysulfone, solvent, hydrophilic additive, non-solvent amount ratio be (15~30): (1~
4): (46~82.5): (1~15): (0.5~5)；
Optionally, the non-solvent includes selected from least one of water, citric acid, acetic acid and phosphoric acid；
Preferably, the non-solvent is water.
10. a kind of method for preparing ultrafiltration membrane, which is characterized in that
1) polyether sulfone, sulfonated polysulfone, solvent, polyethylene glycol, water are stirred to immersion 1~2 hour, the polyethers under the conditions of 25 DEG C
Sulfone, sulfonated polysulfone are previously dried processing, and the drying process is that 2~6h is carried out under conditions of temperature is 40~100 DEG C；
2) mixed liquor after impregnating stirring in step 1) carries out dissolution process, and it is 50~80 DEG C that the dissolution process, which is in temperature,
It carries out 5~6 hours；
3) mixed liquor after dissolution process in step 2) is subjected to standing and defoaming processing, it is 25 that the standing and defoaming processing, which is in temperature,
4~8h is carried out under conditions of~80 DEG C,
4) by standing and defoaming in step 3), treated that mixed liquor carries out blade coating film process, described to scrape to obtain ultrafiltration membrane
Applying film process includes the mixed liquor being coated in braided fabric or template surface, and will be coated in braided fabric or template surface
Mixed liquor carries out striking, evaporation, solidification processing, and the blade coating is to be in temperature with a thickness of the 80-120 μm of evaporation process
10~20s is carried out under the conditions of 12-28 DEG C of air bath, the solidification processing is carried out by coagulating bath, the coagulating bath
Temperature is 5~60 DEG C, and the coagulating bath is water-bath, or the water-bath containing organic solvent, and the organic solvent includes being selected from
In dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide, propyl alcohol, dehydrated alcohol and ethylene glycol
At least one of,
Wherein, the polyether sulfone, sulfonated polysulfone, solvent, hydrophilic additive, non-solvent amount ratio be (15~30): (1~4):
(46~82.5): (1~15): (0.5~5),
The sulfonation degree of the sulfonated polysulfone is 10%-30%, intrinsic viscosity 0.65-0.80dL/g；
The solvent includes being selected from dimethylformamide, dimethyl acetamide, N-Methyl pyrrolidone, dimethyl sulfoxide and phosphorus
At least one of triethylenetetraminehexaacetic acid ester；
The molecular weight of the polyethylene glycol is less than 2000.
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