CN105435660B - A kind of antipollution composite multi-layer polymer separation film and preparation method thereof - Google Patents
A kind of antipollution composite multi-layer polymer separation film and preparation method thereof Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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Abstract
The present invention relates to a kind of antipollution composite multi-layer polymer separation film and preparation method thereof, which has excellent separation function, biocompatibility and contamination resistance.The composite multi-layer polymer separation film is by the multilayered structure with supporting layer and hydrophilic retention functions layer formed thereon, and the interface of hydrophilic retention functions layer and supporting layer is continuous structure.Wherein hydrophilic retention functions layer is the polysulfones based block copolymer composition containing hydrophilic block, and polysulfones family macromolecule is one kind in polysulfones, polyether sulfone, sulfonated polysulfone and polyphenylsulfone.In addition, the hydrophilic retention functions layer surface oxygen element content of composite membrane is more than 17%, there is permanent hydrophilic, do not change with seperation film usage time.The composite multi-layer polymer separation film can be used as supermicro filtration membrane, be also used as nanofiltration, reverse osmosis membrane, forward osmosis membrane basement membrane, be widely used in the separation concentration process in the fields such as biology, medical treatment, electronics and food.
Description
Technical field
The present invention relates to a kind of antipollution composite multi-layer polymer separation films, have excellent separating property, bio-compatible
Property and contamination resistance, can be used for the separation concentration process in the fields such as biology, medical treatment, electronics and food.
Background technology
In recent years, polysulfones ultrafiltration membrane（Including polysulfones, polyether sulfone, sulfonated polysulfone and polyphenylsulfone）By its outstanding performance
It is widely used in all trades and professions.For example, the processing and recycling of industrial wastewater, the purification of town and country drinking water, point of mixed gas
From purification, the separation concentration process of food service industry etc..In addition, the excellent bio-compatibility of PS membrane make its in biomedicine
Through having important application and a foreground, such as at present dialysis, pathogen isolation, man-made organ field carry out application study and
Using.In addition to as ultrafiltration membrane, PS membrane may be used as nanofiltration, reverse osmosis membrane, forward osmosis membrane basement membrane.
However, since polysulfone material itself hydrophily is poor, in membrane separating process, bioseston, macromolecular and colloid are heavy
Product forms Irreversible Adsorption, causes fouling membrane serious easily inside film surface and fenestra, and the anti-organic solvent corrosion of polysulfone material
Poor performance hinders its application in aqueous medium processing；In addition, as polysulfone material uses more and more widely, it is carried
Go out more higher requirements.In order to improve the ability of the anti-organic pollution of polysulfone material, polysulfone material is solved easily by organic solvent
The problem of corrosion and meet various demands of the different industries to polysulfone material, domestic and international chemist is mainly by polysulfones
Material carries out blending and modifying, finished film surface treatment and the modification of membrane material ontology to improve the performance of film.
Patent US5468393 is disclosed with the side of the PS membrane of the fenestra surface modification of hydrophilic vinyl monomer-grafted
Method.This method realizes the grafting of fenestra using the method for ultraviolet radioactive, improves the hydrophily of PS membrane.This method modifying process is multiple
It is miscellaneous, and be affected to the cutoff performance of fenestra and film.Patent 201510566352.8（Nanjing University of Technology）By polysulfones and
The method of inversion of phases prepares modified polysulfone seperation film after hydrophily polysulfones block copolymer is blended, can be by the parent of block copolymer
Water section is embedded in polysulfones seperation film, improves hydrophily.But the method for this blending and modifying, hydrophilic segment is few in film surface distribution, right
The hydrophily of membrane material improves limited.
The present invention is directed to develop a kind of antipollution composite multi-layer polymer separation film, the composite multi-layer polymer separation film by
Multilayered structure with supporting layer and hydrophilic retention functions layer formed thereon, and the boundary of hydrophilic retention functions layer and supporting layer
Face is continuous structure.Wherein hydrophilic retention functions layer is the polysulfones based block copolymer composition containing hydrophilic block.In addition, compound
The hydrophilic retention functions layer surface oxygen element content of film is more than 17 %, has permanent hydrophilic, not with seperation film usage time
Variation.The composite multi-layer polymer separation film has excellent separation function, biocompatibility and contamination resistance, can answer extensively
Separation concentration process for fields such as biology, medical treatment, electronics and food.
The present invention provides the following technical solution：
A kind of antipollution composite multi-layer polymer separation film, which is characterized in that
(a) multilayered structure with supporting layer and hydrophilic retention functions layer formed thereon, and hydrophilic retention functions layer
Interface with supporting layer is continuous structure.
(b) hydrophilic retention functions layer and supporting layer described in are all porous structures, wherein the surface of hydrophilic retention functions layer
Film hole diameter is 1 ~ 500 nanometer, and the surface film hole diameter of supporting layer and hydrophilic retention functions layer bonding part is received for 50 ~ 1000
Rice.Hydrophilic retention functions layer surface film hole diameter is less than support layer surface film hole diameter.
(c) the water infiltration ability of the hydrophilic retention functions layer described in is strong, by water droplet in hydrophilic retention functions layer, 1 second -10 points
Clock（Preferably -1 minute 1 second）Within, water droplet is completely absorbed.The hydrophily of the hydrophilic retention functions layer has permanent
Property, do not change with seperation film usage time.
(d) the hydrophilic retention functions layer main component described in is polysulfones based block copolymer, by hydrophilic block A and polysulfones
Family macromolecule B block has hydrophilic but not soluble in water property by being chemically bonded the block copolymer formed.Wherein hydrophily
Block A is rich oxygen containing high polymer, including polyethylene glycol, polypropylene glycol, poly glycol monomethyl ether, polypropylene glycol monomethyl ether, poly-
Glycolmethacrylate（PEGMA）, polyoxypropylene, polyglycereol, branched polyglycereol, polyvinyl alcohol, POLYPROPYLENE GLYCOL, Portugal are poly-
Sugar, chitosan, hydroxylated polyacrylate etc., polysulfones polymer blocks B are that polysulfones, polyether sulfone, polyphenylsulfone and sulfonation are poly-
One kind in sulfone.
(e) supporting layer described in can coat on base material, can also be not required to base material, make wherein the base material has been enhancing
Polyester fiber non-woven fabric.
(f) composite multi-layer polymer separation film thickness is 50 ~ 300 microns, preferably 80 ~ 300 microns；Wherein hydrophilic retention
Function layer thickness is 100 nanometers ~ 100 microns, accounts for 0.1 ~ 50 %, preferably 10 ~ 20 % of separation film thickness；Support layer thickness
It is 50 ~ 300 microns, accounts for 50 ~ 99 %, preferably 80 ~ 90 % of separation film thickness.
(g) composite multi-layer polymer separation film can be plate membrane or hollow fiber separating film, at 0.1MPa and 25 DEG C
Pure water Penetration ration is more than 100 LMH.
Wherein, the hydrophilic retention functions layer, surface X-ray photoelectron spectroscopic analysis（XPS）Analyze its oxygen element
Content is 17 ~ 40 %, preferably 20 ~ 25 %；And oxygen element content does not change with seperation film usage time, oxygen element mainly comes
Hydrophilic block A in the polysulfones based block copolymer.
Wherein, the plate compounding multiple layer polymer seperation film, preparation process include：
(a) Polymer Solution is coated on polyester fiber non-woven fabric,
(b) make the Polymer Solution containing being immersed in the polyester fiber non-woven fabric, then make the Polymer Solution with
Coagulating bath contacts, and is formed containing the supporting layer being immersed in the polyester fiber non-woven fabric from there through phase separation,
(c) retention functions layer is formed on the supporting layer,
(d) (a) (b) (c) is formed by aqueous solution or alcoholic solution of the nascent state composite multi-layer seperation film at 40 ~ 95 DEG C
Or it is impregnated 5 minutes ~ 24 hours in alcohol water mixed solution.Wherein alcoholic solution is one kind in methanol, ethyl alcohol, propyl alcohol, isopropanol etc.
Or it is a variety of, alcohol water mixed solution is the mixed liquor of the one or more and water in methanol, ethyl alcohol, propyl alcohol, isopropanol etc., wherein water
Volume ratio be 1 ~ 99 %, preferably 60 ~ 90 %.
" impregnation " refers to the state in the fibre gap of porosity support layer infiltration base material wherein in (b).
The manufacturing method of the plate compounding multiple layer polymer seperation film, including be coated with described in formation simultaneously on base material
After the Polymer Solution α of the supporting layer and Polymer Solution β of formation retention functions layer, it is made to contact to occur with coagulating bath
Phase separation.Coating includes state that Polymer Solution α is contacted before reaching base material with Polymer Solution β simultaneously, that is, will be high
When molecular solution α is coated on base material, Polymer Solution β is coated on the state on Polymer Solution α；It is coated with simultaneously and also includes
Polymer Solution α is first coated on base material, and before not entering coagulating bath, Polymer Solution β is coated on Polymer Solution α layers
State.
Wherein, the doughnut composite multi-layer polymer separation film, which is characterized in that preparation process includes：
(a) the middle layer annular that triple channel spinning head is fed after filtering Polymer Solution α and Polymer Solution β respectively is led to
Road and outer annular channel：The middle layer circular passage that Polymer Solution α is wherein fed to triple channel spinning head, by Polymer Solution
β then feeds the outer annular channel of triple channel spinning head；Or, Polymer Solution α is fed to the outer annular channel of triple channel spinning head,
Polymer Solution β is then fed to the middle layer circular passage of triple channel spinning head；
(b) core liquid is fed into triple channel spinning head central tube；
(c) the nascent state hollow fiber composite membrane that a and b step are generated journey is done by 5 ~ 50 centimetres of air bath to immerse
Film-forming in coagulation bath；
(d) that (a) (b) (c) step is formed by nascent state doughnut composite multi-layer seperation film is water-soluble at 40 ~ 95 DEG C
It is impregnated 5 minutes ~ 24 hours in liquid or alcoholic solution or alcohol water mixed solution.Wherein alcoholic solution is methanol, ethyl alcohol, propyl alcohol, isopropanol
One or more in, alcohol water mixed solution is the mixed of the one or more and water in methanol, ethyl alcohol, propyl alcohol, isopropanol etc.
Liquid is closed, the wherein volume ratio of water is 1 ~ 99%, preferably 60 ~ 90 %.
(e) it can be formed in the outer surface of hollow fiber composite membrane through the retention functions layer prepared by (a) (b) (c) (d),
It can be formed in the inner surface of hollow fiber composite membrane, triple channel spinning head is fed after filtering by regulating and controlling Polymer Solution β
Middle layer circular passage or outer annular channel are realized.
Wherein, the Polymer Solution α is different compositions from the Polymer Solution β.It is characterized in that：
(a) the Polymer Solution α described in, by 8 ~ 20 wt.% polysulfones high molecular material a Huo polysulfones based block copolymers
B, 0 ~ 5wt.% cosolvents, 0 ~ 15wt.% pore-foaming agents, 0 ~ 5wt.% non-solvents, 0 ~ 10wt.% surfactants and 45 ~
The compositions such as 92wt.% good solvents.
(b) the Polymer Solution β described in, by 15 ~ 25 wt.% polysulfones based block copolymers b, 0 ~ 5 wt.% cosolvents, 0 ~
The compositions such as 15 wt.% pore-foaming agents, 0 ~ 5 wt.% non-solvents, 0 ~ 10 wt.% surfactants and 40 ~ 85 wt.% good solvents.
(c) the solid component concentration b of the solid component concentration a (weight %) and Polymer Solution β of Polymer Solution α
(weight %) meets the relational expression of a/b≤1.0.
(d) polysulfones high molecular material a is in polysulfones, polyether sulfone, polyphenylsulfone and sulfonated polysulfone in (a) and (b)
It is a kind of.Wherein polysulfones based block copolymer b is the block copolymerization that hydrophilic block A and polysulfones polymer blocks B are bonded together to form
Object has hydrophily but not soluble in water, and the wherein content of hydrophilic block A is 10 ~ 40 %, preferably 15 ~ 30 %.Hydrophilic block
A is rich oxygen containing high polymer, including polyethylene glycol, polypropylene glycol, poly glycol monomethyl ether, polypropylene glycol monomethyl ether, poly- second two
Alcohol methacrylate（PEGMA）, polyoxypropylene, polyvinyl alcohol, POLYPROPYLENE GLYCOL, glucan, chitosan, hydroxylated polypropylene
Hydrochlorate etc..Polysulfones polymer blocks B is one kind in polysulfones, polyether sulfone, polyphenylsulfone and sulfonated polysulfone.
(e) cosolvent, pore-foaming agent, non-solvent, the table of the Polymer Solution β of the Polymer Solution α sums of (a) and (b)
Face activating agent and good solvent can be identical, can also be different.
Wherein, pore-foaming agent is selected from but is not limited only to macromolecule pore-foaming agent and small molecule inorganic salts pore-foaming agent：Macromolecule pore
Agent includes the one or more of polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol etc..Small molecule inorganic salts pore-foaming agent includes
The inorganic salts such as lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, formamide etc. it is one or more.
Non-solvent is selected from but is not limited only to water, hexane, pentane, benzene, toluene, methanol, ethyl alcohol, trichloro ethylene, ethylene glycol, two
Aliphatic hydrocarbons, the fragrance such as polyethylene glycol of ethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, low molecular weight
Hydrocarbon, aliphatic alcohol or their mixed solvent.
Surfactant is selected from but is not limited only to Tween 80, polysorbas20, dodecyl sodium sulfate, dodecyl sodium sulfate etc.
It is one or more.
It is one or more that cosolvent is selected from but is not limited only to dioxane, tributyl phosphate etc..
Good solvent is selected from but is not limited only to n-methyl-2-pyrrolidone (NMP), tetrahydrofuran, dimethyl sulfoxide (DMSO), tetramethyl
Amides, acetone, the methyl ethyl ketone such as sulfoxide, sulfolane, diphenyl sulfone tetramethylurea, dimethylacetylamide, dimethylformamide etc. are low
One or more mixtures of grade alkyl ketone, trimethyl phosphate, the esters such as γ-butyrolactone and lactone etc..
Wherein, the temperature of the coagulating bath, coagulating bath is 10 ~ 90 DEG C, preferably 20 ~ 60 DEG C.The composition of coagulating bath
For water or the mixed solvent of water and organic solvent, wherein organic solvent includes dimethylformamide, dimethylacetylamide, N- first
Or mixtures thereof one kind in base -2-Pyrrolidone, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl sulfone.It mixes molten
The ratio of water is not less than 10 % in agent.
Wherein, the temperature of the core liquid, core liquid is 10 ~ 90 DEG C.The group of coagulating bath become water or organic solvent or water with
The mixed solvent of organic solvent, wherein organic solvent include dimethylformamide, dimethylacetylamide, N- methyl -2- pyrrolidines
Or mixtures thereof one kind in ketone, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl sulfone.
Wherein, the composite multi-layer polymer separation film, can be used as supermicro filtration membrane, be also used as nanofiltration, reverse osmosis
The basement membrane of film, forward osmosis membrane.
Wherein, the composite multi-layer polymer separation film is widely used in the fields such as biology, medical treatment, electronics and food
Separation concentration process, have good hydrophily, biocompatibility and antifouling property.
In addition, the applicant is in patent 201510922936.4（Yantai Institute of Coastal Zone Research, Chinese Academy of Sciences）Middle invention
A kind of preparation method of polysulfones block copolymer, i.e., the polysulfones based block copolymer of the formation retention functions layer involved in patent,
Simply it is described below preparation process.
This method is related to a kind of preparation method of block copolymer, is illustrated with three block ABA type, it is not limited to
ABA type block.A method of the block copolymer of three block being prepared, all blocks belong to ABA types, and wherein block A belongs to
In hydrophilic polymer blocks, B block belongs to polysulfones family, and the two can form block polymer by chemical reaction.Wherein
Polysulfones block has at least 1000 molecular weight, and accounts at least the 50% of block copolymer total amount；B block has at least 100 molecules
Amount, and at least the 1% of block copolymer total amount is accounted for, described method includes following steps：
(I) in the presence of at least one alkali, optionally at least one solvent and further optionally in the presence of entrainer,
By making at least one aromatic diol or aromatic diol salt compound be reacted at least one fragrant dihalo compound, these objects
A kind of sulfone group at least containing there are one in matter, for preparing above-mentioned block copolymer B.
(II) optionally at least one solvent, so that above-mentioned block A mono- is reacted, optionally block the block copolymer B.
(III) block copolymer is recycled in washing.
The beneficial effects of the invention are as follows：
A kind of antipollution composite multi-layer polymer separation film provided by the invention and preparation method thereof, this method preparation process
Simply, the preparation that hydrophily polysulfones block copolymer is realized by polycondensation method, block copolymer and polysulfones-like polymer are matched
Polymer Solution is set, realizes the preparation of hydrophily seperation film.Compared with other methods, manufacture craft is simple, at low cost, and effect is bright
It is aobvious, preparation easy to produce.The preparation clear thinking, it is with obvious effects, at home and abroad still belong to the first.
The preparation clear thinking, it is with obvious effects, at home and abroad still belong to the first.
Specific implementation mode
The polymer separation film of the present invention includes multilayered structure, is divided into hydrophilic layer and supporting layer.It will be close by phase inversion
Water layer is coated on support layer surface preparation.
In the present invention, by the way that block copolymer and polysulfones-like polymer are configured Polymer Solution, hydrophily separation is realized
The preparation of film.
In the preferred embodiment of the present invention, the block copolymer is made by following method：
The preparation of plate membrane：
Polysulfones and block copolymer are added in solvent, Polymer Solution α and Polymer Solution β is respectively configured, in base
Double-mold-head is used on material（Double Slot Die）Coating simultaneously forms the Polymer Solution α of the supporting layer and is formed and retained
After the Polymer Solution β of functional layer, it is made to contact to be separated with coagulating bath.Coating includes Polymer Solution simultaneously
The state that α is contacted before reaching base material with Polymer Solution β, that is, will be high when Polymer Solution α to be coated on base material
Molecular solution β is coated on the state on Polymer Solution A；Coating is also first coated on base material including Polymer Solution α simultaneously,
Before not entering coagulating bath, Polymer Solution β is coated on the state on Polymer Solution α layers.
The preparation of hollow-fibre membrane：
（a）The middle layer annular that triple channel spinning head is fed after Polymer Solution α and Polymer Solution β are filtered respectively is led to
Road and outer annular channel：The middle layer circular passage that Polymer Solution α is wherein fed to triple channel spinning head, by Polymer Solution
β then feeds the outer annular channel of triple channel spinning head；Or, Polymer Solution α is fed to the outer annular channel of triple channel spinning head,
Polymer Solution β is then fed to the middle layer circular passage of triple channel spinning head；
（b）Core liquid is fed into triple channel spinning head central tube；
（c）The nascent state hollow fiber composite membrane that a and b step are generated is done in journey immersion precipitation bath admittedly by air bath
It is melted into film；
（d）It will（a）（b）（c）Step is formed by the water-soluble of nascent state doughnut composite multi-layer seperation film certain temperature
It is impregnated 5 minutes ~ 24 hours in liquid or alcoholic solution or alcohol water mixed solution.
The thickness of hydrophilic layer is found using scanning electron microscopic observation；Film surface composition is analyzed using XPS, contact angle is surveyed
The wellability for trying film carries out flux to seperation film and retention is tested, and investigates the long-term hydrophily of seperation film.
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as to the present invention's
Range is only limitted to example below.Without departing from the idea of the above method of the present invention, known according to ordinary skill
Know the various replacements or change made with customary means, should be included in the scope of the present invention.The method is especially said such as nothing
Bright is conventional method.The material can obtain unless otherwise instructed from open commercial sources.
Embodiment 1
By the polysulfones of 20wt.%, the dioxane of 5wt.%, 5wt.% lithium chlorides, 0.5wt.% water, the Tween 80 of 10wt.%,
59.5wt.%N- N-methyl-2-2-pyrrolidone Ns configure Polymer Solution α；By the polysulfones block ethylene glycol copolymer of 25wt.%,
The tributyl phosphate of 0.5wt.%, 5wt.% propylene glycol, the polysorbas20 of 5wt.%, 64.5wt.% dimethylformamides configure macromolecule
Two kinds of Polymer Solutions are placed in stirring, standing and defoaming at room temperature by solution β.Double-mold-head is used on PET non-woven fabrics（Double
Slot Die）Simultaneously coating formed the supporting layer Polymer Solution α and formed retention functions layer Polymer Solution β it
Afterwards, coagulating bath is immersed（The temperature of coagulating bath is 80 DEG C, and the group of coagulating bath becomes the aqueous solution containing 10% dimethylacetylamide.）
And it is separated.The composite multi-layer seperation film is impregnated 24 hours in 60 DEG C of pure water solution.
Find that hydrophilic retention functions layer accounts for the 30% of entire separation film thickness using scanning electron microscopic observation；Using XPS to film table
Face composition is analyzed, it is found that film surface oxygen element content is 25%, seperation film, by water complete wetting, leads to it within 1 minute
It measures examination and finds that flux up to 600LMHbar, reaches 95% or more, for a long time to the retention of bovine serum albumin（At least three moon）It will divide
It is immersed in the water from film, hydrophily remains unchanged.
Embodiment 2
By the polysulfones of 8wt.%, 92wt.% dimethylacetylamides configure Polymer Solution α；The polysulfones block of 15wt.% is gathered
Ethylene glycol, 85wt.% dimethylformamides configure Polymer Solution β, and Polymer Solution is placed in stirring, standing and defoaming at room temperature.
Double-mold-head is used on PET non-woven fabrics（Double Slot Die）Simultaneously coating formed the supporting layer Polymer Solution α and
It is formed after the Polymer Solution β of retention functions layer, immerses coagulating bath（The temperature of coagulating bath is 10 DEG C, and the group of coagulating bath becomes
Aqueous solution containing 90% dimethylacetylamide.）And it is separated.The composite multi-layer seperation film is contained into 99% first at 80 DEG C
It is impregnated 10 hours in the aqueous solution of alcohol.
Find that hydrophilic retention functions layer accounts for the 10% of entire separation film thickness using scanning electron microscopic observation；Using XPS to film table
Face composition is analyzed, it is found that film surface oxygen element content is 20%, seperation film is within 1 minute by water complete wetting.
Under 0.1Mbar, its flux is tested and finds that flux up to 400LMH, reaches 95% or more, for a long time to the retention of bovine serum albumin
（At least six moon）Seperation film is immersed in the water, hydrophily remains unchanged.
Embodiment 3
By the polysulfones of 20wt.%, 10% PVP (K30), the Tween 80 of 5 wt.%, 65 wt.% dimethyl sulfoxide (DMSO)s configuration high score
Sub- solution α；By the polysulfones block polyethylene glycol of 20wt.%, the tributyl phosphate of 1wt.%, the polysorbas20 of 10wt.%, 69 wt.% bis-
Methylformamide configures Polymer Solution β, and Polymer Solution is placed in stirring, standing and defoaming at room temperature.It is adopted on PET non-woven fabrics
Use Double-mold-head（Double Slot Die）Coating simultaneously forms the Polymer Solution α of the supporting layer and forms retention functions layer
Polymer Solution β after, make its immerse coagulating bath（The temperature of coagulating bath is 20 DEG C, and the group of coagulating bath becomes aqueous solution.）And
It is separated.The composite multi-layer seperation film is impregnated 4 hours in 95 DEG C of aqueous solution.
Find that hydrophilic retention functions layer accounts for the 20% of entire separation film thickness using scanning electron microscopic observation；Using XPS to film table
Face composition is analyzed, it is found that film surface oxygen element content is 35%, seperation film within 1 minute by water complete wetting,
Under 0.1Mbar, its flux is tested and finds that pure water percent of pass reaches 800LMH, 95% or more is reached to the retention of bovine serum albumin, length
Phase（At least 12 months）Seperation film is immersed in the water, hydrophily remains unchanged.
Embodiment 4-12
By the polysulfones-b- polyethylene acid alcohol block copolymers of 15 wt.%, the polysorbas20 of 10 wt.%PEG-400,5wt.%,
70wt.% dimethyl sulfoxide (DMSO)s configure Polymer Solution α；By the polysulfones-b- polyethylene acid alcohol block copolymers of 22wt.%, 1wt.%'s
Tributyl phosphate, the Tween 80 of 6wt.%, 71wt.% dimethylformamides configure Polymer Solution β, Polymer Solution are placed in room
Temperature lower stirring, standing and defoaming.Double-mold-head is used on PET non-woven fabrics（Double Slot Die）Coating forms the branch simultaneously
It supports the Polymer Solution α of layer and is formed after the Polymer Solution β of retention functions layer, immerse coagulating bath（The temperature of coagulating bath is
20 DEG C, the group of coagulating bath becomes the aqueous solution containing 5% dimethylformamide.）It is separated.By the composite multi-layer seperation film
It is impregnated 2 hours in 95 DEG C of aqueous solution.
Using scanning electron microscopic observation composite separating film, the surface film hole diameter of hydrophilic retention functions layer is 5 ~ 10 nanometers, branch
The surface film hole diameter for supportting layer and hydrophilic retention functions layer bonding part is 50 ~ 100 nanometers.Its flux is tested, as a result such as
Table 1.
Table 1
Following embodiment is the preparation of hollow fiber separating film.
Embodiment 13
By the polysulfones of 20wt.%, the dioxane of 5wt.%, 8wt.%PEG400,0.5wt.% water, the Tween 80 of 5wt.%,
61.5wt.%N- N-methyl-2-2-pyrrolidone Ns configure Polymer Solution α；By the polysulfones block polyethylene glycol of 25wt.%, 0.5wt.%'s
Tributyl phosphate, 1wt.% propylene glycol, the polysorbas20 of 5wt.%, 68.5wt.% dimethylformamides configure Polymer Solution β, will be high
Molecular solution is placed in stirring, standing and defoaming at room temperature.Threeway is fed after Polymer Solution α and Polymer Solution β are filtered respectively
The middle layer circular passage of road spinning head and outer annular channel：Polymer Solution α is wherein fed to the centre of triple channel spinning head
Polymer Solution β, then is fed the outer annular channel of triple channel spinning head by layer circular passage.50% dimethylacetylamide will be contained
Aqueous solution（Core liquid）It feeds in triple channel spinning head central tube, core liquid temperature is 80 DEG C, and nascent state doughnut is compound
Film does film-forming in journey immersion precipitation bath by air bath；The temperature of coagulating bath is 60 DEG C, and the group of coagulating bath, which becomes, contains 10%
The aqueous solution of dimethylacetylamide.
Find that hydrophilic retention functions layer accounts for the 50% of entire separation film thickness using scanning electron microscopic observation；Using XPS to film table
Face composition is analyzed, it is found that film surface oxygen element content is 25%, seperation film within 1 minute by water complete wetting,
Under 0.1MPar pressure, its flux is tested and finds that pure water Penetration ration up to 400LMH, reaches 95% to the retention of bovine serum albumin
More than, for a long time（At least one moon）Seperation film is immersed in the water, hydrophily remains unchanged.
Embodiment 14
By the polysulfones of 15wt.%, 88wt.%N- N-methyl-2-2-pyrrolidone Ns configure Polymer Solution α；By the polysulfones of 20wt.%
Block polyethylene glycol, 80wt.% dimethylformamides configure Polymer Solution β, and Polymer Solution is placed in and stirs at room temperature, is quiet
Set deaeration.After Polymer Solution α and Polymer Solution β are filtered respectively feed triple channel spinning head middle layer circular passage and
Outer annular channel：The outer annular channel that Polymer Solution α is fed to triple channel spinning head, threeway is then fed by Polymer Solution β
The middle layer circular passage of road spinning head.By the aqueous solution containing 99% dimethylformamide（Core liquid）Feed triple channel spinning head
In central tube, core liquid temperature is 10 DEG C, and nascent state hollow fiber composite membrane is done in journey immersion precipitation bath admittedly by air bath
It is melted into film；The temperature of coagulating bath is 80 DEG C, and the group of coagulating bath becomes the aqueous solution containing 50% dimethylacetylamide.
Find that hydrophilic retention functions layer accounts for the 0.1% of entire separation film thickness using scanning electron microscopic observation；Using XPS to film
Surface composition is analyzed, it is found that film surface oxygen element content is 17%, seperation film is within 1 minute by water complete wetting.
Under 0.1MPar pressure, its flux is tested and finds that pure water Penetration ration up to 700LMH, reaches 95% to the retention of bovine serum albumin
More than, for a long time（At least six moon）Seperation film is immersed in the water, hydrophily remains unchanged.
Embodiment 15-23
By the polysulfones of 20wt.%, the dioxane of 5wt.%, 0.5wt.% ethylene glycol, the Tween 80 of 10wt.%, 64.5wt.%
N-methyl-2-pyrrolidone configures Polymer Solution α；By the polysulfones block polyethylene glycol of 25wt.%, the tricresyl phosphate fourth of 5wt.%
Ester, 5wt.% polyvinylpyrrolidone, 5wt.% propylene glycol, 60wt.% dimethylformamides configure Polymer Solution β, will be high
Molecular solution is placed in stirring, standing and defoaming at room temperature.Threeway is fed after Polymer Solution α and Polymer Solution β are filtered respectively
The middle layer circular passage of road spinning head and outer annular channel：Polymer Solution α is wherein fed to the centre of triple channel spinning head
Polymer Solution β, then is fed the outer annular channel of triple channel spinning head by layer circular passage.40% dimethylacetylamide will be contained
Aqueous solution（Core liquid）It feeds in triple channel spinning head central tube, core liquid temperature is 40 DEG C, and nascent state doughnut is compound
Film does film-forming in journey immersion precipitation bath by air bath；The temperature of coagulating bath is 40 DEG C, and the group of coagulating bath, which becomes, contains 65%
The aqueous solution of dimethylacetylamide.
Find that hydrophilic layer accounts for entire separation film thickness using scanning electron microscopic observation；Film surface composition is divided using XPS
Analysis, result such as table 2.
Table 2
It should be noted last that the above specific implementation mode is merely illustrative of the technical solution of the present invention and unrestricted,
Although being described the invention in detail with reference to example, it will be understood by those of ordinary skill in the art that, it can be to the present invention
Technical solution be modified or replaced equivalently, without departing from the spirit of the technical scheme of the invention and range, should all cover
In the scope of the claims of the present invention.
Claims (10)
1. a kind of antipollution composite multi-layer polymer separation film, which is characterized in that
(a) multilayered structure with supporting layer and hydrophilic retention functions layer formed thereon, and hydrophilic retention functions layer and branch
The interface for supportting layer is continuous structure；
(b) hydrophilic retention functions layer and supporting layer described in are all porous structures, wherein the surface fenestra of hydrophilic retention functions layer
A diameter of 1 ~ 500 nanometer, the surface film hole diameter of supporting layer and hydrophilic retention functions layer bonding part is 50 ~ 1000 nanometers, hydrophilic
Retention functions layer surface film hole diameter is less than support layer surface film hole diameter；
(c) the water infiltration ability of the hydrophilic retention functions layer described in is strong, by water droplet in hydrophilic retention functions layer, -10 minutes 1 second it
Interior, water droplet is completely absorbed, and the hydrophily of the hydrophilic retention functions layer has permanently, not with seperation film usage time
Variation；
(d) the hydrophilic retention functions layer main component described in is polysulfones based block copolymer, by hydrophilic block A and polysulfones high score
Sub- B block has hydrophilic but not soluble in water property, wherein hydrophilic block A by being chemically bonded the block copolymer formed
It is rich oxygen containing high polymer, including polyethylene glycol, polypropylene glycol, poly glycol monomethyl ether, polypropylene glycol monomethyl ether, polyethylene glycol
Methacrylate, polyoxypropylene, polyvinyl alcohol, POLYPROPYLENE GLYCOL, glucan, chitosan, hydroxylated polyacrylate, polysulfones
Family macromolecule B block is one kind in polysulfones, polyether sulfone, polyphenylsulfone and sulfonated polysulfone, (e) described in supporting layer can be on base material
It coats, wherein the base material has been the polyester fiber non-woven fabric of humidification；
(f) composite multi-layer polymer separation film thickness is 50 ~ 300 microns；Wherein hydrophilic retention functions layer thickness be 100 nanometers ~
100 microns；It is 50 ~ 300 microns to support layer thickness；
(g) composite multi-layer polymer separation film can be plate membrane or hollow fiber separating film, the pure water at 0.1 MPa and 25 DEG C
Penetration ration is more than 10 LMH.
2. composite multi-layer polymer separation film according to claim 1, which is characterized in that the hydrophilic retention functions layer,
Its surface X-ray photoelectron spectroscopic analysis（XPS）It is 17 ~ 40% to analyze its oxygen element content；And oxygen element content is not with separation
Film usage time and change, oxygen element is mainly derived from the hydrophilic block A in the polysulfones based block copolymer.
3. a kind of preparation method of composite multi-layer polymer separation film as claimed in claim 1 or 2, which is characterized in that described
The preparation process of plate compounding multiple layer polymer seperation film includes：
(a) Polymer Solution is coated on polyester fiber non-woven fabric,
(b) make the Polymer Solution containing being immersed in the polyester fiber non-woven fabric, then make the Polymer Solution and solidification
Bath contact is formed from there through phase separation containing the supporting layer being immersed in the polyester fiber non-woven fabric,
(c) hydrophilic retention functions layer is formed on the supporting layer,
(d) (a) (b) (c) is formed by aqueous solution or alcoholic solution or alcohol water of the nascent state composite multi-layer seperation film at 40 ~ 95 DEG C
It is impregnated in mixed solution 5 minutes ~ 24 hours, wherein alcoholic solution is one or more, the alcohol in methanol, ethyl alcohol, propyl alcohol, isopropanol
Water mixed solution is the mixed liquor of the one or more and water in methanol, ethyl alcohol, propyl alcohol, isopropanol, the wherein volume ratio of water
It is 1 ~ 99%,
" impregnation " refers to the state that porosity support layer penetrates into substrate fiber gap wherein in (b).
4. the preparation method of composite multi-layer polymer separation film according to claim 3, which is characterized in that the step packet
It includes on base material while coating forms the Polymer Solution α of the supporting layer and forms the Polymer Solution of hydrophilic retention functions layer
After β, it is made to be contacted with coagulating bath to be separated, at the same coating include Polymer Solution α before reaching base material and
The state of Polymer Solution β contacts, that is, when Polymer Solution α to be coated on base material, Polymer Solution β is coated on height
State on molecular solution α；Coating is also first coated on base material including Polymer Solution α simultaneously, will be high before not entering coagulating bath
Molecular solution β is coated on the state on Polymer Solution α layers.
5. the preparation method of multiple layer polymer seperation film according to claim 4, which is characterized in that the doughnut is multiple
Closing multiple layer polymer seperation film preparation process includes：
(a) after Polymer Solution α and Polymer Solution β being filtered respectively feed triple channel spinning head middle layer circular passage and
Outer annular channel：Polymer Solution α is wherein fed to the middle layer circular passage of triple channel spinning head, then by Polymer Solution β
Feed the outer annular channel of triple channel spinning head；Or, Polymer Solution α is fed to the outer annular channel of triple channel spinning head, it will
Polymer Solution β then feeds the middle layer circular passage of triple channel spinning head；
(b) core liquid is fed into triple channel spinning head central tube；
(c) will（a）With（b）The nascent state hollow fiber composite membrane that step generates is done journey and immersed by 1 ~ 50 centimetre of air bath to coagulate
Gu film-forming in bath；
(d) will（a）（b）With（c）Step is formed by aqueous solution of the nascent state doughnut composite multi-layer seperation film at 40 ~ 95 DEG C
Or impregnated in alcoholic solution or alcohol water mixed solution 5 minutes ~ 24 hours, wherein alcoholic solution is in methanol, ethyl alcohol, propyl alcohol, isopropanol
It is one or more, alcohol water mixed solution is the mixed liquor of methanol, ethyl alcohol, propyl alcohol, one or more and water in isopropanol,
The volume ratio of middle water is 1 ~ 99%；
(e) it passes through（a）（b）（c）（d）Prepared hydrophilic retention functions layer can be formed in the outer surface of hollow fiber composite membrane,
It can be formed in the inner surface of hollow fiber composite membrane, triple channel spinning head is fed after filtering by regulating and controlling Polymer Solution β
Middle layer circular passage or outer annular channel are realized.
6. the preparation method of composite multi-layer polymer separation film according to claim 4 or 5, it is characterised in that：Macromolecule
Solution α is different compositions from the Polymer Solution β：
(a) the Polymer Solution α described in, by 8 ~ 20 wt.% polysulfones high molecular material a or polysulfones based block copolymer b, 0 ~
5wt.% cosolvents, 0 ~ 15wt.% pore-foaming agents, 0 ~ 5wt.% non-solvents, 0 ~ 10wt.% surfactants and 45 ~ 92wt.% are good
Solvent forms；
(b) the Polymer Solution β described in, by 15 ~ 25 wt.% polysulfones based block copolymers b, 0 ~ 5wt.% cosolvents, 0 ~
15wt.% pore-foaming agents, 0 ~ 5wt.% non-solvents, 0 ~ 10wt.% surfactants and 40 ~ 85wt.% good solvents composition；
(c) the solid component concentration b (weights of the solid component concentration a (weight %) and Polymer Solution β of Polymer Solution α
Amount %) meet the relational expressions of a/b≤1.0；
(d) (a) and polysulfones high molecular material a in (b) are one in polysulfones, polyether sulfone, polyphenylsulfone and sulfonated polysulfone
Kind, wherein polysulfones based block copolymer b is the block copolymer that hydrophilic block A and polysulfones polymer blocks B are bonded together to form,
With hydrophily but not soluble in water, the wherein content of hydrophilic block A is 10 ~ 40%, and hydrophilic block A is rich oxygen containing high polymer,
Including polyethylene glycol, polypropylene glycol, poly glycol monomethyl ether, polypropylene glycol monomethyl ether, polyethylene glycol methacrylate-styrene polymer, polyoxy
Propylene, polyvinyl alcohol, POLYPROPYLENE GLYCOL, glucan, chitosan, hydroxylated polyacrylate, polysulfones polymer blocks B is poly-
One kind in sulfone, polyether sulfone, polyphenylsulfone and sulfonated polysulfone,
(e) cosolvent of the Polymer Solution β of the Polymer Solution α sums of (a) and (b), pore-foaming agent, non-solvent, surface are lived
Property agent and good solvent can be identical, can also be different；
Wherein, pore-foaming agent is selected from but is not limited only to macromolecule pore-foaming agent and small molecule inorganic salts pore-foaming agent：Macromolecule pore-foaming agent packet
Include polyethylene glycol, polyvinylpyrrolidone, polyvinyl alcohol it is one or more, small molecule inorganic salts pore-foaming agent includes chlorination
Lithium, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, formamide it is one or more；
Non-solvent is selected from but is not limited only to water, hexane, pentane, benzene, toluene, methanol, ethyl alcohol, trichloro ethylene, ethylene glycol, diethyl two
The polyethylene glycol of alcohol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexylene glycol, low molecular weight；
Surfactant is selected from but is not limited only to Tween 80, polysorbas20, dodecyl sodium sulfate it is one or more；
It is one or more that cosolvent is selected from but is not limited only to dioxane, tributyl phosphate；
It is sub- that good solvent is selected from but is not limited only to n-methyl-2-pyrrolidone (NMP), tetrahydrofuran, dimethyl sulfoxide (DMSO), tetramethyl
Amides, acetone, the methyl ethyl ketone such as sulfone, sulfolane, diphenyl sulfone tetramethylurea, dimethylacetylamide, dimethylformamide.
7. the preparation method of the composite multi-layer polymer separation film according to claim 3 or 4 or 5, which is characterized in that solidification
The temperature of bath is 10 ~ 90 DEG C, and the group of coagulating bath becomes the mixed solvent of water or water and organic solvent, and wherein organic solvent includes two
Methylformamide, dimethylacetylamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl
The ratio of or mixtures thereof one kind in sulfone, in the mixed solvent water is not less than 10%.
8. the preparation method of composite multi-layer polymer separation film according to claim 5, which is characterized in that the temperature of core liquid
It it is 10 ~ 90 DEG C, the group of coagulating bath becomes the mixed solvent of water or organic solvent or water and organic solvent, and wherein organic solvent includes
Dimethylformamide, dimethylacetylamide, n-methyl-2-pyrrolidone, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, hexichol
Or mixtures thereof one kind in base sulfone.
9. composite multi-layer polymer separation film according to claim 1 or 2, can be used as supermicro filtration membrane, it is also used as receiving
Filter, reverse osmosis membrane, forward osmosis membrane basement membrane.
10. composite multi-layer polymer separation film according to claim 1 or 2, be widely used in biology, medical treatment, electronics and
The separation concentration process of field of food.
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