CN105435660A - Anti-pollution composite multi-layer polymer separation membrane and preparation method thereof - Google Patents
Anti-pollution composite multi-layer polymer separation membrane and preparation method thereof Download PDFInfo
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- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
- B01D69/02—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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- 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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- 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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- B01D71/06—Organic material
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Abstract
The invention relates to an anti-pollution composite multi-layer polymer separation membrane and a preparation method thereof. The separation membrane has excellent separation function, biocompatibility and anti-pollution capacity. The composite multi-layer polymer separation membrane is of a multi-layer structure including a support layer and a hydrophilic interception functional layer, wherein the multi-layer structure is formed on the support layer, and the interface between the hydrophilic interception functional layer and the support layer is of a continuous structure; the hydrophilic interception functional layer is formed by polysulfone segmented copolymers containing hydrophilic blocks, and polysulfone macromolecules are one of polysulfone, polyether sulfone, sulfonated polysulfone and polyethylene sulfone. Besides, the content of oxygen element on the surface of the hydrophilic interception functional layer of the composite membrane is more than 17%, and the composite membrane has permanent hydrophily which is not changed along with the use time of the separation membrane. The composite multi-layer polymer separation membrane can be used as a super-micro filtration membrane as well as base membranes of nanofiltration membranes, reverse osmosis membranes and forward osmosis membranes and can be widely applied to the separation and concentration processes in the fields of biology, medical treatment, electrons, foods and the like.
Description
Technical field
The present invention relates to a kind of antipollution composite multi-layer polymer separation film, have excellent separating property, biocompatibility and contamination resistance, what can be used for the fields such as biology, medical treatment, electronics and food is separated concentration process.
Background technology
In recent years, polysulfones milipore filter (comprising polysulfones, polyether sulfone, SPSF and PPSU) is widely used in all trades and professions by means of its outstanding performance.Such as, the disposal and recovery of industrial wastewater, water purification is drunk in town and country, the separating-purifying of mist, the separation concentration process etc. of food service industry.In addition, the bio-compatibility of PS membrane excellence makes it in biomedicine, have important application and prospect, as carried out application study and application in fields such as dialysis, pathogen isolation, man-made organs at present.Except as except milipore filter, PS membrane can be used as the basement membrane of nanofiltration, reverse osmosis membrane, forward osmosis membrane.
But, because polysulfone material self hydrophily is poor, in membrane separating process, bioseston, large molecule and colloidal deposition easily film surface and fenestra inner, form Irreversible Adsorption, cause fouling membrane serious, and polysulfone material anti-organic solvent corrosive nature is poor, hinders its application in aqueous medium process; In addition, along with polysulfone material uses more and more widely, more higher requirements are proposed to it.In order to improve the ability of the anti-Organic Pollution of polysulfone material, solve problem that polysulfone material easily corroded by organic solvent and meet the various demands of different industries to polysulfone material, domestic and international chemist mainly through polysulfone material is carried out blending and modifying, finished film surface treatment and membrane material body modification to improve the performance of film.
Patent US5468393 discloses with the method for the PS membrane of the fenestra surface modification of hydrophilic vinyl monomer-grafted.The method utilizes the method for ultra-violet radiation to realize the grafting of fenestra, improves the hydrophily of PS membrane.The method modifying process is complicated, and larger on the cutoff performance impact of fenestra and film.Patent 201510566352.8(Nanjing University of Technology) prepare modified polysulfone diffusion barrier by the method for polysulfones and the blended rear inversion of phases of hydrophily polysulfones block copolymer, the hydrophilic section of block copolymer can be embedded polysulfones diffusion barrier, improve hydrophily.But the method for this blending and modifying, hydrophilic segment is few in film surface distributed, improves limited to the hydrophily of membrane material.
The present invention is intended to develop a kind of antipollution composite multi-layer polymer separation film, this composite multi-layer polymer separation film is by the sandwich construction 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 block copolymer composition containing hydrophilic block.In addition, the hydrophilic retention functions layer Surface Oxygen constituent content of composite membrane is greater than 17%, has permanent hydrophilic, does not change with diffusion barrier service time.This composite multi-layer polymer separation film has excellent separation function, and biocompatibility and contamination resistance, what can be widely used in the fields such as biology, medical treatment, electronics and food is separated concentration process.
The invention provides following technical scheme:
A kind of antipollution composite multi-layer polymer separation film, is characterized in that,
A () has the sandwich construction of supporting layer and hydrophilic retention functions layer formed thereon, and the interface of hydrophilic retention functions layer and supporting layer is continuous structure.
B the hydrophilic retention functions layer described in () and supporting layer are all loose structures, wherein the skin covering of the surface bore dia of hydrophilic retention functions layer is 1 ~ 500 nanometer, and the skin covering of the surface bore dia of supporting layer and hydrophilic retention functions layer bonding part is 50 ~ 1000 nanometers.Hydrophilic retention functions layer skin covering of the surface bore dia 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 at hydrophilic retention functions layer, within 1 second-10 minutes (being preferably 1 second-1 minute), water droplet is completely absorbed.The hydrophily of described hydrophilic retention functions layer has permanent, does not change with diffusion barrier service time.
D the supporting layer described in () can apply and form on base material, also can not need base material, and wherein said base material has been the polyester fiber non-woven fabric of humidification.
E () composite multi-layer polymer separation film thickness is 50 ~ 300 microns, be preferably 80 ~ 300 microns; Wherein hydrophilic retention functions layer thickness is 100 nanometer ~ 100 micron, accounts for 0.1 ~ 50% of diffusion barrier thickness, is preferably 10 ~ 20%; Supporting layer thickness is 50 ~ 300 microns, accounts for 50 ~ 99% of diffusion barrier thickness, is preferably 80 ~ 90%.
F () composite multi-layer polymer separation film can be Flat Membrane or hollow fiber separating film, the pure water Penetration ration at 0.1MPa and 25 DEG C is greater than 100LMH.
Wherein, the hydrophilic retention functions layer of described composite multi-layer polymer separation film, it is 17 ~ 40% that its surface X-ray photoelectron spectroscopic analysis (XPS) analyzes its oxygen element content, is preferably 20 ~ 25%; And oxygen element content does not change with diffusion barrier service time.
Wherein, described plate compounding multiple layer polymer diffusion barrier, preparation process comprises:
A Polymer Solution is coated on polyester fiber non-woven fabric by (),
B () makes described Polymer Solution containing being immersed in described polyester fiber non-woven fabric, then make described Polymer Solution contact with coagulating bath, is formed containing the supporting layer be immersed in described polyester fiber non-woven fabric thus by being separated,
C () forms retention functions layer on described supporting layer,
D nascent state composite multi-layer diffusion barrier that (a) (b) (c) is formed by () soaks 5 minutes ~ 24 hours in the aqueous solution of 40 ~ 95 DEG C or alcoholic solution or alcohol water mixed solution.Wherein alcoholic solution is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc., and alcohol water mixed solution is the mixed liquor of one or more and water in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc., and wherein the volume ratio of water is 1 ~ 99%, is preferably 60 ~ 90%.
Wherein in (b), " impregnation " refers to that porous supporting layer infiltrates the state in the fibre gap of base material.
The manufacture method of described plate compounding multiple layer polymer diffusion barrier, after the Polymer Solution α being included in the described supporting layer of coating formation simultaneously on base material and the Polymer Solution β forming retention functions layer, makes it contact with coagulating bath thus be separated.Coating simultaneously comprises the state that Polymer Solution α contacted with Polymer Solution β before arriving base material, that is, when being coated on base material by Polymer Solution α, Polymer Solution β is coated on the state on Polymer Solution α; Be coated with simultaneously and also comprise Polymer Solution α and be first coated on base material, before not entering coagulating bath, Polymer Solution β is coated on the state on Polymer Solution α layer.
Wherein, described doughnut composite multi-layer polymer separation film, it is characterized in that, preparation process comprises:
A Polymer Solution α and Polymer Solution β is filtered circular passage, intermediate layer and the outer annular channel of rear infeed triple channel spinning head by () respectively: the circular passage, intermediate layer wherein Polymer Solution α being fed triple channel spinning head, then feeds the outer annular channel of triple channel spinning head by Polymer Solution β; Or, by the outer annular channel that Polymer Solution α feeds triple channel spinning head, Polymer Solution β is then fed the circular passage, intermediate layer of triple channel spinning head;
B core liquid is fed triple channel spinning head central tube by ();
C nascent state hollow fiber composite membrane that a and b step produce by () does film-forming in the bath of journey immersion precipitation through the air bath of 5 ~ 50 centimetres;
D nascent state doughnut composite multi-layer diffusion barrier that (a) (b) (c) step is formed by () soaks 5 minutes ~ 24 hours in the aqueous solution of 40 ~ 95 DEG C or alcoholic solution or alcohol water mixed solution.Wherein alcoholic solution is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc., and alcohol water mixed solution is the mixed liquor of one or more and water in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc., and wherein the volume ratio of water is 1 ~ 99%, is preferably 60 ~ 90%.
E () can be formed at the outer surface of hollow fiber composite membrane through the retention functions layer prepared by (a) (b) (c) (d), also can be formed at the inner surface of hollow fiber composite membrane, be fed circular passage, intermediate layer or the outer annular channel realization of triple channel spinning head by regulation and control Polymer Solution β after filtering.
Wherein, described Polymer Solution α is different compositions from described Polymer Solution β.It is characterized in that:
Polymer Solution α described in (a), by 8 ~ 20wt.% polysulfones macromolecular material a or polysulfones block copolymer b, 0 ~ 5wt.% cosolvent, 0 ~ 15wt.% pore-foaming agent, 0 ~ 5wt.% non-solvent, 0 ~ 10wt.% surfactant and 45 ~ 92wt.% good solvent etc. form.
B the Polymer Solution β described in (), is made up of 15 ~ 25wt.% polysulfones block copolymer b, 0 ~ 5wt.% cosolvent, 0 ~ 15wt.% pore-foaming agent, 0 ~ 5wt.% non-solvent, 0 ~ 10wt.% surfactant and 40 ~ 85wt.% good solvent etc.
C the solid component concentration a (% by weight) of () Polymer Solution α and the solid component concentration b (% by weight) of Polymer Solution β meet the relational expression of a/b≤1.0.
D () described (a) and (b) middle polysulfones macromolecular material a is the one in polysulfones, polyether sulfone, PPSU and SPSF.Wherein polysulfones block copolymer b is the block copolymer that hydrophilic block A and polysulfones polymer blocks B institute bonding are formed, and has hydrophily but water insoluble, and wherein the content of hydrophilic block A is 10 ~ 40%, is preferably 15 ~ 30%.Hydrophilic block A is rich oxygen containing high polymer, comprise polyethylene glycol, polypropylene glycol, poly glycol monomethyl ether, polypropylene glycol monomethyl ether, polyethylene glycol methacrylate-styrene polymer (PEGMA), polyoxypropylene, polyvinyl alcohol, POLYPROPYLENE GLYCOL, glucan, shitosan, hydroxylated polyacrylate etc.Polysulfones polymer blocks B is the one in polysulfones, polyether sulfone, PPSU and SPSF.
The Polymer Solution α of (e) described (a) and (b) and the cosolvent of Polymer Solution β, pore-foaming agent, non-solvent, surfactant and good solvent can be identical, also can be different.
Wherein, pore-foaming agent is selected from but is not limited only to macromolecule pore-foaming agent and Small molecular inorganic salts pore-foaming agent: macromolecule pore-foaming agent comprises one or more of polyethylene glycol, PVP, polyvinyl alcohol etc.Small molecular inorganic salts pore-foaming agent comprises the inorganic salts such as lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, one or more of formamide etc.
Non-solvent is selected from but is not limited only to aliphatic hydrocarbon, aromatic hydrocarbon, aliphatic alcohol or their mixed solvents such as water, hexane, pentane, benzene, toluene, methyl alcohol, ethanol, trichloro-ethylene, ethylene glycol, diethylene glycol, triethylene glycol, propane diols, butanediol, pentanediol, hexylene glycol, low-molecular-weight polyethylene glycol.
Surfactant is selected from but is not limited only to Tween 80, polysorbas20, one or more of dodecyl sodium sulfate, dodecyl sodium sulfate etc.
Cosolvent be selected from but be not limited only to dioxane, tributyl phosphate etc. one or more.
Good solvent is selected from but is not limited only to one or more mixtures of ester and the lactones etc. such as the lower alkyl ketone such as acid amides, acetone, MEK, trimethyl phosphate, gamma-butyrolacton such as METHYLPYRROLIDONE (NMP), oxolane, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl sulfone tetramethylurea, dimethylacetylamide, dimethyl formamide.
Wherein, described coagulating bath, the temperature of coagulating bath is 10 ~ 90 DEG C, is preferably 20 ~ 60 DEG C.The mixed solvent consisting of water or water and organic solvent of coagulating bath, wherein organic solvent comprises one in dimethyl formamide, dimethylacetylamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl sulfone or its mixture.In mixed solvent, the ratio of water is not less than 10%.
Wherein, described core liquid, the temperature of core liquid is 10 ~ 90 DEG C.The mixed solvent consisting of water or organic solvent or water and organic solvent of coagulating bath, wherein organic solvent comprises one in dimethyl formamide, dimethylacetylamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl sulfone or its mixture.
Wherein, described composite multi-layer polymer separation film, can be used as supermicro filtration membrane, also can be used as the basement membrane of nanofiltration, reverse osmosis membrane, forward osmosis membrane.
Wherein, described composite multi-layer polymer separation film, what be widely used in the fields such as biology, medical treatment, electronics and food is separated concentration process, has 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) in invented a kind of preparation method of polysulfones block copolymer, the polysulfones block copolymer of the formation retention functions layer namely related in patent, is simply described below preparation process.
This method relates to a kind of preparation method of block copolymer, illustrates, but be not limited in ABA type block with three block ABA type.Prepare a method for the block copolymer of three blocks, all blocks all belong to ABA type, and wherein block A belongs to 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 50% of block copolymer total amount; B block has at least 100 molecular weight, and accounts at least 1% of block copolymer total amount, and described method comprises the steps:
(I) under at least one alkali exists, optional at least one solvent and optional under entrainer exists further, react by making at least one aromatic diol or aromatic diol salt compound and at least one fragrance dihalo compound, one in these materials at least containing a sulfuryl group, is used for preparing above-mentioned block copolymer B.
(II) optional at least one solvent, above-mentioned block A mono-is reacted, block copolymer B described in optional end-blocking.
(III) block copolymer described in washing and recycling.
The invention has the beneficial effects as follows:
A kind of antipollution composite multi-layer polymer separation film provided by the invention and preparation method thereof, the method preparation process is simple, the preparation of hydrophily polysulfones block copolymer is realized by polycondensation method, by block copolymer and polysulfones-like polymer configuration Polymer Solution, realize the preparation of hydrophily diffusion barrier.Compared with additive method, manufacture craft is simple, and cost is low, successful, easy manufacture.This prepares clear thinking, successful, still belongs to the first at home and abroad.
This prepares clear thinking, successful, still belongs to the first at home and abroad.
Detailed description of the invention
Polymer separation film of the present invention comprises sandwich construction, is divided into hydrophilic layer and supporting layer.By phase inversion, hydrophilic layer is coated on support layer surface preparation.
In the present invention, by by block copolymer and polysulfones-like polymer configuration Polymer Solution, realize the preparation of hydrophily diffusion barrier.
Of the present invention one preferred embodiment in, described block copolymer by following method obtain:
The preparation of Flat Membrane:
Polysulfones and block copolymer are added in solvent, configure Polymer Solution α and Polymer Solution β respectively, base material uses after Double-mold-head (DoubleSlotDie) is coated with the Polymer Solution α forming described supporting layer and the Polymer Solution β forming retention functions layer simultaneously, make it contact with coagulating bath thus be separated.Coating simultaneously comprises the state that Polymer Solution α contacted with Polymer Solution β before arriving base material, that is, when being coated on base material by Polymer Solution α, Polymer Solution β is coated on the state on Polymer Solution A; Be coated with simultaneously and also comprise Polymer Solution α and be first coated on base material, before not entering coagulating bath, Polymer Solution β is coated on the state on Polymer Solution α layer.
The preparation of hollow-fibre membrane:
A Polymer Solution α and Polymer Solution β is filtered circular passage, intermediate layer and the outer annular channel of rear infeed triple channel spinning head by () respectively: the circular passage, intermediate layer wherein Polymer Solution α being fed triple channel spinning head, then feeds the outer annular channel of triple channel spinning head by Polymer Solution β; Or, by the outer annular channel that Polymer Solution α feeds triple channel spinning head, Polymer Solution β is then fed the circular passage, intermediate layer of triple channel spinning head;
B core liquid is fed triple channel spinning head central tube by ();
C nascent state hollow fiber composite membrane that a and b step produce by () does film-forming in the bath of journey immersion precipitation through air bath;
Soak 5 minutes ~ 24 hours in the aqueous solution of d nascent state doughnut composite multi-layer diffusion barrier uniform temperature that (a) (b) (c) step is formed by () or alcoholic solution or alcohol water mixed solution.
Scanning electron microscopic observation is used to find the thickness of hydrophilic layer; Use XPS to analyze film surface composition, the wellability of contact angle test membrane, flux carried out to diffusion barrier and retains test, and investigating the long-term hydrophily of diffusion barrier.
Below by way of specific embodiment, the present invention is described in further detail, but this should be interpreted as scope of the present invention is only limitted to following example.When not departing from said method thought of the present invention, the various replacement made according to ordinary skill knowledge and customary means or change, all should be within the scope of the present invention.Described method is conventional method if no special instructions.Described material all can obtain from open commercial sources if no special instructions.
Embodiment 1
By the polysulfones of 20wt.%, the dioxane of 5wt.%, 5wt.% lithium chloride, 0.5wt.% water, the Tween 80 of 10wt.%, 59.5wt.%N-N-methyl-2-2-pyrrolidone N-configuration Polymer Solution α; By the polysulfones block ethylene glycol copolymer of 25wt.%, the tributyl phosphate of 0.5wt.%, 5wt.% propane diols, the polysorbas20 of 5wt.%, two kinds of Polymer Solutions are placed in stirred at ambient temperature, standing and defoaming by 64.5wt.% dimethyl formamide configuration Polymer Solution β.PET non-woven fabrics adopt after Double-mold-head (DoubleSlotDie) is coated with the Polymer Solution α forming described supporting layer and the Polymer Solution β forming retention functions layer simultaneously, (temperature of coagulating bath is 80 DEG C, the aqueous solution consisted of containing 10% dimethylacetylamide of coagulating bath to immerse coagulating bath.) and be separated.This composite multi-layer diffusion barrier is soaked 24 hours in the pure water solution of 60 DEG C.
Scanning electron microscopic observation is used to find that hydrophilic retention functions layer accounts for 30% of whole diffusion barrier thickness; XPS is used to analyze film surface composition, find that film Surface Oxygen constituent content is 25%, diffusion barrier within 1 minute by water complete wetting, the test of its flux is found that flux can reach 600LMHbar, more than 95% is reached to retaining of bovine serum albumin, diffusion barrier is immersed in the water by (at least 3 months) for a long time, and hydrophily remains unchanged.
Embodiment 2
By the polysulfones of 8wt.%, 92wt.% dimethylacetylamide configuration Polymer Solution α; By the polysulfones block polyethylene glycol of 15wt.%, 85wt.% dimethyl formamide configuration Polymer Solution β, is placed in stirred at ambient temperature, standing and defoaming by Polymer Solution.PET non-woven fabrics adopt after Double-mold-head (DoubleSlotDie) is coated with the Polymer Solution α forming described supporting layer and the Polymer Solution β forming retention functions layer simultaneously, (temperature of coagulating bath is 10 DEG C, the aqueous solution consisted of containing 90% dimethylacetylamide of coagulating bath to immerse coagulating bath.) and be separated.This composite multi-layer diffusion barrier was soaked 10 hours 80 DEG C contain in the aqueous solution of 99% methyl alcohol.
Scanning electron microscopic observation is used to find that hydrophilic retention functions layer accounts for 10% of whole diffusion barrier thickness; Use XPS to analyze film surface composition, find that film Surface Oxygen constituent content is 20%, diffusion barrier within 1 minute by water complete wetting.Under 0.1Mbar, find that flux can reach 400LMH to the test of its flux, reach more than 95% to retaining of bovine serum albumin, diffusion barrier is immersed in the water by long-term (at least 6 months), and hydrophily remains unchanged.
Embodiment 3
By the polysulfones of 20wt.%, 10%PVP (K30), the Tween 80 of 5wt.%, 65wt.% dimethyl sulfoxide (DMSO) configuration Polymer Solution α; By the polysulfones block polyethylene glycol of 20wt.%, the tributyl phosphate of 1wt.%, the polysorbas20 of 10wt.%, 69wt.% dimethyl formamide configuration Polymer Solution β, is placed in stirred at ambient temperature, standing and defoaming by Polymer Solution.PET non-woven fabrics adopt after Double-mold-head (DoubleSlotDie) is coated with the Polymer Solution α forming described supporting layer and the Polymer Solution β forming retention functions layer simultaneously, make its immerse coagulating bath (temperature of coagulating bath is 20 DEG C, coagulating bath consist of the aqueous solution.) and be separated.This composite multi-layer diffusion barrier is soaked 4 hours in the aqueous solution of 95 DEG C.
Scanning electron microscopic observation is used to find that hydrophilic retention functions layer accounts for 20% of whole diffusion barrier thickness; XPS is used to analyze film surface composition, find that film Surface Oxygen constituent content is 35%, diffusion barrier within 1 minute by water complete wetting, under 0.1Mbar, the test of its flux is found that pure water percent of pass reaches 800LMH, reach more than 95% to retaining of bovine serum albumin, diffusion barrier is immersed in the water by long-term (at least 12 months), and hydrophily remains unchanged.
Embodiment 4-12
By the polysulfones-b-polyethylene acid alcohol block copolymer of 15wt.%, the polysorbas20 of 10wt.%PEG-400,5wt.%, 70wt.% dimethyl sulfoxide (DMSO) configuration Polymer Solution α; By the polysulfones-b-polyethylene acid alcohol block copolymer of 22wt.%, the tributyl phosphate of 1wt.%, the Tween 80 of 6wt.%, 71wt.% dimethyl formamide configuration Polymer Solution β, is placed in stirred at ambient temperature, standing and defoaming by Polymer Solution.PET non-woven fabrics adopt after Double-mold-head (DoubleSlotDie) is coated with the Polymer Solution α forming described supporting layer and the Polymer Solution β forming retention functions layer simultaneously, (temperature of coagulating bath is 20 DEG C, the aqueous solution consisted of containing 5% dimethyl formamide of coagulating bath to immerse coagulating bath.) be separated.This composite multi-layer diffusion barrier is soaked 2 hours in the aqueous solution of 95 DEG C.
Use scanning electron microscopic observation composite separating film, the skin covering of the surface bore dia of hydrophilic retention functions layer is 5 ~ 10 nanometers, and the skin covering of the surface bore dia of supporting layer and hydrophilic retention functions layer bonding part is 50 ~ 100 nanometers.Test its flux, result is as table 1.
Table 1
Following examples are 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 N-configuration Polymer Solution α; By the polysulfones block polyethylene glycol of 25wt.%, the tributyl phosphate of 0.5wt.%, 1wt.% propane diols, the polysorbas20 of 5wt.%, 68.5wt.% dimethyl formamide configuration Polymer Solution β, is placed in stirred at ambient temperature, standing and defoaming by Polymer Solution.Polymer Solution α and Polymer Solution β is filtered respectively circular passage, intermediate layer and the outer annular channel of rear infeed triple channel spinning head: the circular passage, intermediate layer wherein Polymer Solution α being fed triple channel spinning head, then feeds the outer annular channel of triple channel spinning head by Polymer Solution β.Feed in triple channel spinning head central tube by the aqueous solution (core liquid) containing 50% dimethylacetylamide, core liquid temp is 80 DEG C, and nascent state hollow fiber composite membrane is done film-forming in the bath of journey immersion precipitation through air bath; The temperature of coagulating bath is 60 DEG C, the aqueous solution consisted of containing 10% dimethylacetylamide of coagulating bath.
Scanning electron microscopic observation is used to find that hydrophilic retention functions layer accounts for 50% of whole diffusion barrier thickness; XPS is used to analyze film surface composition, find that film Surface Oxygen constituent content is 25%, diffusion barrier within 1 minute by water complete wetting, under 0.1MPar pressure, the test of its flux is found that pure water Penetration ration can reach 400LMH, reach more than 95% to retaining of bovine serum albumin, diffusion barrier is immersed in the water by long-term (at least 1 month), and hydrophily remains unchanged.
Embodiment 14
By the polysulfones of 15wt.%, 88wt.%N-N-methyl-2-2-pyrrolidone N-configuration Polymer Solution α; By the polysulfones block polyethylene glycol of 20wt.%, 80wt.% dimethyl formamide configuration Polymer Solution β, is placed in stirred at ambient temperature, standing and defoaming by Polymer Solution.Polymer Solution α and Polymer Solution β is filtered respectively circular passage, intermediate layer and the outer annular channel of rear infeed triple channel spinning head: the outer annular channel that Polymer Solution α is fed triple channel spinning head, then feeds the circular passage, intermediate layer of triple channel spinning head by Polymer Solution β.Feed in triple channel spinning head central tube by the aqueous solution (core liquid) containing 99% dimethyl formamide, core liquid temp is 10 DEG C, and nascent state hollow fiber composite membrane is done film-forming in the bath of journey immersion precipitation through air bath; The temperature of coagulating bath is 80 DEG C, the aqueous solution consisted of containing 50% dimethylacetylamide of coagulating bath.
Scanning electron microscopic observation is used to find that hydrophilic retention functions layer accounts for 0.1% of whole diffusion barrier thickness; Use XPS to analyze film surface composition, find that film Surface Oxygen constituent content is 17%, diffusion barrier within 1 minute by water complete wetting.Under 0.1MPar pressure, find that pure water Penetration ration can reach 700LMH to the test of its flux, reach more than 95% to retaining of bovine serum albumin, diffusion barrier is immersed in the water by long-term (at least 6 months), and 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-N-methyl-2-2-pyrrolidone N-configuration Polymer Solution α; By the polysulfones block polyethylene glycol of 25wt.%, the tributyl phosphate of 5wt.%, 5wt.% PVP, 5wt.% propane diols, 60wt.% dimethyl formamide configuration Polymer Solution β, is placed in stirred at ambient temperature, standing and defoaming by Polymer Solution.Polymer Solution α and Polymer Solution β is filtered respectively circular passage, intermediate layer and the outer annular channel of rear infeed triple channel spinning head: the circular passage, intermediate layer wherein Polymer Solution α being fed triple channel spinning head, then feeds the outer annular channel of triple channel spinning head by Polymer Solution β.Feed in triple channel spinning head central tube by the aqueous solution (core liquid) containing 40% dimethylacetylamide, core liquid temp is 40 DEG C, and nascent state hollow fiber composite membrane is done film-forming in the bath of journey immersion precipitation through air bath; The temperature of coagulating bath is 40 DEG C, the aqueous solution consisted of containing 65% dimethylacetylamide of coagulating bath.
Hydrophilic layer accounts for whole diffusion barrier thickness to use scanning electron microscopic observation to find; Use XPS to analyze film surface composition, its result is as table 2.
Table 2
It should be noted last that, above detailed description of the invention is only in order to illustrate technical scheme of the present invention and unrestricted, although with reference to example to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to technical scheme of the present invention or equivalent replacement, and not departing from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of right of the present invention.
Claims (10)
1. an antipollution composite multi-layer polymer separation film, is characterized in that,
A () has the sandwich construction of supporting layer and hydrophilic retention functions layer formed thereon, and the interface of hydrophilic retention functions layer and supporting layer is continuous structure;
B the hydrophilic retention functions layer described in () and supporting layer are all loose structures, wherein the skin covering of the surface bore dia of hydrophilic retention functions layer is 1 ~ 500 nanometer, the skin covering of the surface bore dia of supporting layer and hydrophilic retention functions layer bonding part is 50 ~ 1000 nanometers, and hydrophilic retention functions layer skin covering of the surface bore dia 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 at hydrophilic retention functions layer, within 1 second-10 minutes (being preferably 1 second-1 minute), water droplet is completely absorbed, the hydrophily of described hydrophilic retention functions layer has permanent, does not change with diffusion barrier service time;
D the supporting layer described in () can apply and form on base material, also can not need base material, and wherein said base material has been the polyester fiber non-woven fabric of humidification;
E () composite multi-layer polymer separation film thickness is 50 ~ 300 microns, be preferably 80 ~ 300 microns; Wherein hydrophilic retention functions layer thickness is 100 nanometer ~ 100 micron, accounts for 0.1 ~ 50% of diffusion barrier thickness, is preferably 10 ~ 20%; Supporting layer thickness is 50 ~ 300 microns, accounts for 50 ~ 99% of diffusion barrier thickness, is preferably 80 ~ 90%;
F () composite multi-layer polymer separation film can be Flat Membrane or hollow fiber separating film, the pure water Penetration ration at 0.1MPa and 25 DEG C is greater than 100LMH.
2. composite multi-layer polymer separation film according to claim 1, is characterized in that, described hydrophilic retention functions layer, and it is 17 ~ 40% that its surface X-ray photoelectron spectroscopic analysis (XPS) analyzes its oxygen element content, is preferably 20 ~ 25%; And oxygen element content does not change with diffusion barrier service time.
3. the preparation method of composite multi-layer polymer separation film according to claim 1 and 2, is characterized in that, the preparation process of described plate compounding multiple layer polymer diffusion barrier comprises:
A Polymer Solution is coated on polyester fiber non-woven fabric by (),
B () makes described Polymer Solution containing being immersed in described polyester fiber non-woven fabric, then make described Polymer Solution contact with coagulating bath, is formed containing the supporting layer be immersed in described polyester fiber non-woven fabric thus by being separated,
C () forms retention functions layer on described supporting layer,
D nascent state composite multi-layer diffusion barrier that (a) (b) (c) is formed by () soaks 5 minutes ~ 24 hours in the aqueous solution of 40 ~ 95 DEG C or alcoholic solution or alcohol water mixed solution, wherein alcoholic solution is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc., alcohol water mixed solution is the mixed liquor of one or more and water in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc., wherein the volume ratio of water is 1 ~ 99%, be preferably 60 ~ 90%
Wherein in (b), " impregnation " refers to that porous supporting layer infiltrates the state in substrate fiber gap.
4. prepare the preparation method of composite multi-layer polymer separation film according to claim 3, it is characterized in that, after described step is included in the Polymer Solution α of the described supporting layer of coating formation simultaneously on base material and the Polymer Solution β of formation retention functions layer, it is made to contact with coagulating bath thus be separated, coating simultaneously comprises the state that Polymer Solution α contacted with Polymer Solution β before arriving base material, namely, when being coated on base material by Polymer Solution α, Polymer Solution β is coated on the state on Polymer Solution α; Be coated with simultaneously and also comprise Polymer Solution α and be first coated on base material, before not entering coagulating bath, Polymer Solution β is coated on the state on Polymer Solution α layer.
5. the preparation method of multiple layer polymer diffusion barrier according to claim 1, is characterized in that, described doughnut composite multi-layer polymer separation film preparation process comprises:
A Polymer Solution α and Polymer Solution β is filtered circular passage, intermediate layer and the outer annular channel of rear infeed triple channel spinning head by () respectively: the circular passage, intermediate layer wherein Polymer Solution α being fed triple channel spinning head, then feeds the outer annular channel of triple channel spinning head by Polymer Solution β; Or, by the outer annular channel that Polymer Solution α feeds triple channel spinning head, Polymer Solution β is then fed the circular passage, intermediate layer of triple channel spinning head;
B core liquid is fed triple channel spinning head central tube by ();
C nascent state hollow fiber composite membrane that (a) and (b) step produce by () does film-forming in the bath of journey immersion precipitation through the air bath of 1 ~ 50 centimetre;
D nascent state doughnut composite multi-layer diffusion barrier that (a) (b) and (c) step are formed by () soaks 5 minutes ~ 24 hours in the aqueous solution of 40 ~ 95 DEG C or alcoholic solution or alcohol water mixed solution, wherein alcoholic solution is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc., alcohol water mixed solution is the mixed liquor of one or more and water in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol etc., wherein the volume ratio of water is 1 ~ 99%, is preferably 60 ~ 90%;
E () can be formed at the outer surface of hollow fiber composite membrane through the retention functions layer prepared by (a) (b) (c) (d), also can be formed at the inner surface of hollow fiber composite membrane, be fed circular passage, intermediate layer or the outer annular channel realization of triple channel spinning head by regulation and control Polymer Solution β after filtering.
6. the preparation method of the composite multi-layer polymer separation film according to claim 4 or 5, is characterized in that: Polymer Solution α is different compositions from described Polymer Solution β:
(a) Polymer Solution α according to claim 4, by 8 ~ 20wt.% polysulfones macromolecular material a or polysulfones block copolymer b, 0 ~ 5wt.% cosolvent, 0 ~ 15wt.% pore-foaming agent, 0 ~ 5wt.% non-solvent, 0 ~ 10wt.% surfactant and 45 ~ 92wt.% good solvent etc. form;
B () Polymer Solution β according to claim 4, is made up of 15 ~ 25wt.% polysulfones block copolymer b, 0 ~ 5wt.% cosolvent, 0 ~ 15wt.% pore-foaming agent, 0 ~ 5wt.% non-solvent, 0 ~ 10wt.% surfactant and 40 ~ 85wt.% good solvent etc.;
C the solid component concentration a (% by weight) of () Polymer Solution α and the solid component concentration b (% by weight) of Polymer Solution β meet the relational expression of a/b≤1.0;
D () described (a) and (b) middle polysulfones macromolecular material a is polysulfones, polyether sulfone, one in PPSU and SPSF, wherein polysulfones block copolymer b is the block copolymer that hydrophilic block A and polysulfones polymer blocks B institute bonding are formed, there is hydrophily but water insoluble, wherein the content of hydrophilic block A is 10 ~ 40%, be preferably 15 ~ 30%, hydrophilic block A is rich oxygen containing high polymer, comprise polyethylene glycol, polypropylene glycol, poly glycol monomethyl ether, polypropylene glycol monomethyl ether, polyethylene glycol methacrylate-styrene polymer (PEGMA), polyoxypropylene, polyvinyl alcohol, POLYPROPYLENE GLYCOL, glucan, shitosan, hydroxylated polyacrylate etc., polysulfones polymer blocks B is polysulfones, polyether sulfone, one in PPSU and SPSF,
The Polymer Solution α of (e) described (a) and (b) and the cosolvent of Polymer Solution β, pore-foaming agent, non-solvent, surfactant and good solvent can be identical, also can be different;
Wherein, pore-foaming agent is selected from but is not limited only to macromolecule pore-foaming agent and Small molecular inorganic salts pore-foaming agent: macromolecule pore-foaming agent comprises one or more of polyethylene glycol, PVP, polyvinyl alcohol etc., Small molecular inorganic salts pore-foaming agent comprises the inorganic salts such as lithium chloride, sodium chloride, calcium chloride, lithium nitrate, formaldehyde, one or more of formamide etc.;
Non-solvent is selected from but is not limited only to aliphatic hydrocarbon, aromatic hydrocarbon, aliphatic alcohol or their mixed solvents such as water, hexane, pentane, benzene, toluene, methyl alcohol, ethanol, trichloro-ethylene, ethylene glycol, diethylene glycol, triethylene glycol, propane diols, butanediol, pentanediol, hexylene glycol, low-molecular-weight polyethylene glycol;
Surfactant is selected from but is not limited only to Tween 80, polysorbas20, one or more of dodecyl sodium sulfate, dodecyl sodium sulfate etc.;
Cosolvent be selected from but be not limited only to dioxane, tributyl phosphate etc. one or more;
Good solvent is selected from but is not limited only to one or more mixtures of ester and the lactones etc. such as the lower alkyl ketone such as acid amides, acetone, MEK, trimethyl phosphate, gamma-butyrolacton such as METHYLPYRROLIDONE (NMP), oxolane, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl sulfone tetramethylurea, dimethylacetylamide, dimethyl formamide.
7. the preparation method of the composite multi-layer polymer separation film according to claim 3 or 4 or 5, it is characterized in that, the temperature of coagulating bath is 10 ~ 90 DEG C, be preferably 20 ~ 60 DEG C, the mixed solvent consisting of water or water and organic solvent of coagulating bath, wherein organic solvent comprises one in dimethyl formamide, dimethylacetylamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl sulfone or its mixture, and in mixed solvent, the ratio of water is not less than 10%.
8. the preparation method of composite multi-layer polymer separation film according to claim 5, it is characterized in that, the temperature of core liquid is 10 ~ 90 DEG C, the mixed solvent consisting of water or organic solvent or water and organic solvent of coagulating bath, wherein organic solvent comprises one in dimethyl formamide, dimethylacetylamide, METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), tetramethyl sulfoxide, sulfolane, diphenyl sulfone or its mixture.
9. the composite multi-layer polymer separation film according to claim 1,2,3,4 or 5, can be used as supermicro filtration membrane, also can be used as the basement membrane of nanofiltration, reverse osmosis membrane, forward osmosis membrane.
10., according to claim 1, the composite multi-layer polymer separation film described in 2,3,4 and 5, what be widely used in the fields such as biology, medical treatment, electronics and food is separated concentration process.
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