CN106943899A - A kind of hydrophilic polysulfone film and preparation method thereof - Google Patents
A kind of hydrophilic polysulfone film and preparation method thereof Download PDFInfo
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- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01D67/0013—Casting processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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- 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
- B01D69/06—Flat membranes
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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
- B01D69/08—Hollow fibre membranes
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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
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention relates to a kind of hydrophilic polysulfone film and preparation method thereof, it is characterised in that it is characterized in that the DOPA amine layer on the composite membrane and coating composite membrane that are made up of polysulfones-like polymer, acrylonitrile maleic anhydride polymer is constituted.Using polysulfones-like polymer as membrane material, by adding a small amount of acrylonitrile maleic anhydride polymer into preparation liquid, because this polymer contains substantial amounts of carboxyl, hydrophily is to significantly improve.Repeatedly coated, while further improving its hydrophilicity, the aperture of film is further reduced, significantly improved by modification with the hydrophily of caudacoria, the aperture of film is faded to the scope of nanofiltration by ultrafiltration using dopamine afterwards.Using such a NF membrane can allow inorganic salts and small molecule by and dyestuff macromolecular be trapped the characteristics of, can be applied to dye desalination process, by modified film be used for direct red desalination, rejection be 80~99%.
Description
Technical field
The present invention relates to a kind of preparation field of organic film, and in particular to a kind of hydrophilic polysulfone film and its preparation side
Method, i.e. polysulfones be film hydrophilically modified and its research of aperture modification.
Background technology
Dye industry is the important component of chemical industry, and it occupies an important position in national economy, traditional
Art production process not only produces a large amount of high salinity, high chroma, high COD waste water severe contamination environment, and salting-out process is brought into
Salinity reduce the purity of dyestuff, influence the dissolubility and coloring of dyestuff.Nanofiltration membrane treatment technology is between ultrafiltration and anti-
The membrane separating process using pressure as driving force between infiltration, the relative molecular mass of most of water-soluble dyes is just in nanofiltration
The retention phase of film to molecular weight range within, dye solution by NF membrane in being circulated, and part water and salt will transmit through film, and
Dye molecule is rejected by, by the way that toward the washing that adds water in system, salinity will gradually lower in feed liquid.
Polysulfones-like polymer is a kind of unbodied high-performance engineering polymer, and with excellent performance, such as intensity is high, change
Learn stability and hydrolytic stability is good etc., due to its good stability so that polysulfones-like polymer turns into a kind of well resistance to
Solvent organic film material.Due to its higher surface chemistry energy so that film surface hydrophilic performance is poor, causes fouling membrane serious.
Fouling membrane is to influence the matter of utmost importance of fouling membrane process, and it is flux rapid decay and to be difficult to clean in film running that it, which is showed,
Recover, be also the limitation wide variety of bottleneck of membrane separation technique, the maximally effective method of the problem of solving above-mentioned is to carry out parent to film
Water is modified.At present, the method for conventional raising film surface hydrophilicity has adsorption of modification method, surface coating modified method, blending and modifying
Method, low-temperature plasma modified method, illumination graft modification method etc..For the modification of polysulfones film, CN106179002A is disclosed
A kind of poly- tertiary amine of polysulfones side chain graft, the method for preparing microfiltration membranes.CN105817147A disclose it is a kind of using polyethylene glycol with
Silica is combined modified polysulfone film.CN105771707A discloses a kind of using amphiphilic block polymer polymethylacrylic acid sulphur
Sour choline-polymethyl methacrylate-polymethylacrylic acid sulfonic acid choline (PSBMA-b-PMMA-b-PSBMA) blending and modifying gathers
Ether sulfone film, hydrophily is improved.
In existing technology, there are some defects in polysulfones film：
1st, polysulfones film hydrophily is poor, and polluter is easily adsorbed during use, makes small membrane flux, short life, easily blocks up
Plug, reduction treatment effeciency, promote the use of it and receive very big limitation；
2nd, the preparation method of existing polysulfones NF membrane is all the method using interfacial polymerization, and operating process is complicated, molten
Agent consumption is big, and utilization rate of equipment and installations is low, it can be seen that, the preparation of the polysulfones film of prior art is remained to be further improved.
The content of the invention
The invention aims to further improve the hydrophily and separating property of polysulfones film, especially for sewage
Handle and a kind of hydrophilic polysulfone film and preparation method thereof is provided.The polysulfones pollution resistant composite film of proposition not only has high
Rejection, and anti-fouling performance is good, has potential development in sewage treatment area.
Technical scheme：
The present invention is modified using two methods of blending modification method, surface coating modified method to polysulfones film, by with
Acrylonitrile-maleic anhydride polymer blending, the hydrophily of film is significantly improved, and is then coated by dopamine after being modified,
The hydrophilicity of film is further improved, also, using the stronger adhesion property of dopamine, the hole on film surface is modified, and is improved
The separating effect of film, realizes transformation of the aperture of film from ultrafiltration to nanofiltration, while the aperture of film is effectively reduced, further
Improve the hydrophily of film.
The present invention concrete technical scheme be：A kind of hydrophilic polysulfone film, it is characterised in that by polysulfones-like polymer, third
DOPA amine layer composition on the composite membrane and coating composite membrane of alkene nitrile-maleic anhydride polymer composition, wherein composite membrane
Supporting layer thickness is 10~300 μm, and separating layer thickness is 0.1~0.5 μm, and the thickness of DOPA amine layer is about 50~500nm, modified
Retaining molecular weight afterwards is 500~4,000Da.
It is preferred that above-mentioned polysulfones-like polymer is polysulfones, polyether sulfone, PPSU or polyarylsulfone (PAS), wherein polysulfones molecular weight is 1,
700~3,500Da, polyether sulfone molecular weight are 1,000~6,020Da, and PPSU molecular weight is 3,000~5,000Da, polyarylsulfone (PAS)
Molecular weight is 1,000~7,700Da.
Present invention also offers the preparation method of above-mentioned hydrophilic polysulfone film, it is comprised the following steps that：
(A) preparation liquid is prepared
Polysulfones-like polymer, organic additive, inorganic additive and acrylonitrile-maleic anhydride polymer is dissolved in are had
In machine solvent, it is well mixed and prepares casting solution raw material, wherein, the mass content of polysulfones-like polymer is 15~25%, You Jitian
Plus the mass content that the mass content of agent is 0.1~15%, inorganic additive is 0.1~5%, acrylonitrile-maleic anhydride
Polymer content 0.1~5%；Organic solvent 50%~84.7%；
(B) preparation of film
The preparation of film is divided into the preparation of Flat Membrane or hollow-fibre membrane：
The preparation method of Flat Membrane：Temperature be 15~30 DEG C, humidity be 30~70% under, step (A) is prepared
Preparation liquid is poured on clean glass plate, and the thickness of regulation scraper is 10~300 μm, and knifing speed is 5~50mmin-1, it is empty
3~20s of residence time in gas, the film scraped is put into coagulating bath (deionized water) together with glass plate, controls coagulation bath temperature
For 10~50 DEG C, after being handled through rinsing, polysulfones composite membrane is obtained；
The preparation method of hollow-fibre membrane：Temperature be 15~30 DEG C, humidity be 30~70% under, by step (A) prepare
Good supporting layer casting solution injects spinning solution and core liquid in binary channels spinning head, the injection of its SMIS liquid as spinning solution simultaneously
Core passage, spinning solution injection outer layer channel, extrusion prepares 3~20s of residence time in hollow-fibre membrane idiosome, air, will
The doughnut idiosome of preparation is put into coagulating bath (deionized water), and it is 10~50 DEG C to control coagulation bath temperature；
(C) dopamine repeatedly coats polysulfones composite membrane
The preparation of Tris (trishydroxymethylaminomethane)-HCl buffer solutions：Prepare 0.01~1molL-1Tris solution,
PH to 1~9 is adjusted with hydrochloric acid, dopamine is then added into buffer solution, dopamine concentration is 1~6gL-1, by answering for preparing
Close film to be put into dopamine solution, be put into shaking table concussion 6~24h of coating, afterwards, take the film out, or be put into newly prepare many
Coated again in bar amine aqueous solution, obtain hydrophilic polysulfone film.
It is preferred that above-mentioned organic additive molecular weight is 10,000~360,000Da polyvinylpyrrolidone or molecular weight
For one kind in 200~10,000Da polyethylene glycol or any several combination.
It is preferred that above-mentioned inorganic additive is titanium oxide, aluminum oxide, zinc oxide, zirconium oxide or lithium chloride.
It is preferred that above-mentioned organic solvent be N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE,
Dimethyl sulfoxide (DMSO) or acetone.
It is preferred that the rate of extrusion of the preparation process SMIS liquid of hollow-fibre membrane is 1~20 ml/min, spinning solution extrusion
Speed is 1~18 ml/min.
It is preferred that the core liquid described in the preparation process of hollow-fibre membrane is deionized water and the mixture of solvent；Wherein solvent
For N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) or acetone；Core liquid reclaimed water
Content account for 20~50%.
The number of times coated again in preferred steps C is 1~10 time.
Above-mentioned acrylonitrile-maleic anhydride polymer is preferred to use conventional aqueous polymerization process and prepared：
With potassium peroxydisulfate (K2S2O8) and sodium sulfite (Na2SO3) it is chain initiator, acrylonitrile (AN) and maleic anhydride
(MAH) it is monomer, reacts and reacted in 70 DEG C, nitrogen atmosphere.Equipped with reflux condensing tube, air inlet pipe and agitating device
In there-necked flask, AN, MAH, K are added according to certain order2S2O8、Na2SO3And deionized water (uses 0.05molL-1's
H2SO4Adjust pH to 3), whisked using certain rotating speed agitator make solution be well mixed, reaction 5h after take out sediment, successively with nothing
Water-ethanol, deionized water are respectively washed three times, are dried after vacuum filtration at 60 DEG C, and weigh.
Beneficial effect：
(1) acrylonitrile-maleic anhydride polymer contains hydrophilic functional group's carboxyl, has with polysulfones-like polymer good
Good compatibility so that the polysulfones film prepared has good hydrophily, and antifouling property is good, in the process of inversion of phases
The hydrophilic segment of middle acrylonitrile-maleic anhydride polymer can spontaneously move to film surface and occur self assembly effect, film
Hydrophily and anti-fouling performance are greatly enhanced.
(2) composite membrane is coated using dopamine, on the one hand due to the good hydrophily of dopamine, further increases film
Antifouling property, on the other hand, due to the stronger adhesion property of dopamine so that form one layer of compacted zone on film surface, rises
To the effect of modification membrane aperture, the separating property of film is improved.
Embodiment
Further the present invention is illustrated below by specific embodiment, but the present invention is not limited only to this.
Embodiment 1
This method prepares a kind of hydrophily PPSU dye desalination membrane material.By the polyethylene pyrrole that molecular weight is 10,000Da
Pyrrolidone, acrylonitrile-maleic anhydride, titanium dioxide and molecular weight are dissolved in N, N- dimethyl for 3,000Da PPSU
It is well mixed to be configured to casting solution raw material in formamide, wherein, the mass content of polyvinylpyrrolidone is 15%, PPSU
Mass content be 15%, the content of acrylonitrile-maleic anhydride is 5%, and content of titanium dioxide is 0.1%, N, N- diformazans
The mass content of base formamide is 64.9%.It is 15 DEG C to control room temperature, and humidity is 30%, and preparation liquid is equably poured on into glass plate
On, the height of regulation scraper is 10 μm, and knifing speed is 5mmin-1.It is put into and fills after film stops 3s in atmosphere after having scraped
(50 DEG C) carry out rinsing processing after film idiosome film-forming and after departing from glass plate in the coagulating bath of deionized water, are changed once per 4h
Water, changes after 3 times and carries out characterization test to film.Prepare 0.01molL-1Tris cushioning liquid 1L, with hydrochloric acid adjust pH to 1, Xiang Huan
Addition 1g dopamines in solution are rushed, the composite membrane prepared is put into dopamine solution, shaking table concussion coating 24h is put into, takes
Concussion cleaning 3 times in deionized water are put into after going out.
Obtained composite membrane contact angle is 30 °, and supporting layer thickness is 10 μm, and separating layer thickness is 0.1 μm, DOPA amine layer
Thickness be 50nm.At 0.5MPa and 25 DEG C, pure water flux 20Lm is determined with ultrafiltration apparatus-2·h-1, PEG retention molecules
Measure as 4,000Da, using 100mgL-1Directly red/NaCl salting liquids filtering, salt ion can pass through, to direct red
Rejection is 80%.
Embodiment 2
This method prepares a kind of hydrophily PPSU dye desalination membrane material.By the polyethylene pyrrole that molecular weight is 36,000Da
Pyrrolidone, acrylonitrile-maleic anhydride, molecular weight are dissolved in N for 5,000Da PPSU and zirconium dioxide nanoparticles,
It is well mixed to be configured to casting solution raw material in N- dimethylacetylamides, wherein, the mass content of polyvinylpyrrolidone is
0.1%, the mass content of PPSU is 25%, and the content of acrylonitrile-maleic anhydride is 0.1%, zirconium dioxide nanometer
Grain content is 5%, and the mass content of DMF is 69.8%,.It is 30 DEG C to control room temperature, and humidity is 70%.Will
The casting solution prepared is used as spinning solution, 80% acetone and 20% deionized water mixture injection core passageway, the extrusion of core liquid
Speed is 20 ml/mins, and the rate of extrusion of casting solution is 18 ml/mins.By 20s airspace, into coagulating bath
(10 DEG C) solidifications, form double-layer hollow fiber film, are collected by up- coiler.The hollow-fibre membrane prepared is immersed in deionization
In water, a water is changed per 4h, changes after 3 times and characterization test is carried out to film.Prepare 1molL-1Tris cushioning liquid 1L, use hydrochloric acid
PH to 9 is adjusted, 2g dopamines are added into cushioning liquid, the composite membrane prepared is put into dopamine solution, shaking table shake is put into
Coating 6h is swung, afterwards, is taken the film out, is placed again into the dopamine solution newly prepared and coats again, so circulation coating 10
It is secondary, concussion cleaning 3 times in deionized water are put into after taking-up.
Obtained composite membrane contact angle is 20 °, and supporting layer thickness is 250 μm, and separating layer thickness is 0.5 μm, dopamine
The thickness of layer is 500nm.At 0.5MPa and 25 DEG C, pure water flux 8Lm is determined with ultrafiltration apparatus-2·h-1, PEG retentions point
Son amount is 500Da, using 100mgL-1Directly red/NaCl salting liquids filtering, salt ion can pass through, to direct red
Rejection is 99%.
Embodiment 3
This method prepares a kind of hydrophily polysulfones dye desalination membrane material.Polysulfones that molecular weight is 3,500Da, molecular weight are
55,000Da polyvinylpyrrolidone, acrylonitrile-maleic anhydride and inorganic particulate zirconium oxide is dissolved in dimethyl sulfoxide (DMSO),
It is well mixed to be configured to casting solution raw material, wherein, the mass content of polysulfones is 25%, the content of acrylonitrile-maleic anhydride
For 1%, the content of aluminum oxide is 2.5%, and polyvinyl pyrrolidone content is 15%, and the content of 1-METHYLPYRROLIDONE is
56.5%.It is 30 DEG C to control room temperature, and humidity is 70%, by preparation liquid equably on a glass, and the height of regulation scraper is
300 μm, knifing speed is 50mmin-1.The coagulating bath for filling deionized water is put into after having scraped after film stops 15s in atmosphere
In (25 DEG C) rinsing processing is carried out after film idiosome film-forming and after departing from glass plate, change a water per 4h, film entered after changing 3 times
Row characterization test.Prepare 0.2molL-1Tris cushioning liquid 1L, with hydrochloric acid adjust pH to 2, into cushioning liquid add 6g it is many
Bar amine, the composite membrane prepared is put into dopamine solution, is put into shaking table concussion coating 10h, afterwards, is taken the film out, again
It is put into the dopamine solution newly prepared and coats again, so circulation coating 9 times, is put into after taking-up in deionized water and shakes clear
Wash 3 times.
Obtained composite membrane contact angle is 20 °, and supporting layer thickness is 300 μm, and separating layer thickness is 0.3 μm, dopamine
The thickness of layer is 450nm.At 0.5MPa and 25 DEG C, pure water flux 9Lm is determined with ultrafiltration apparatus-2·h-1, PEG retentions point
Son amount is 550Da, using 100mgL-1Directly red/NaCl salting liquids filtering, salt ion can pass through, to direct red
Rejection is 98%.
Embodiment 4
This method prepares a kind of hydrophily polysulfones dye desalination membrane material.Polysulfones, molecular weight by molecular weight for 1,700Da
It is 360,000Da polyvinylpyrrolidone, acrylonitrile-maleic anhydride and alumina dissolution in 1-METHYLPYRROLIDONE,
It is well mixed to be configured to casting solution raw material, wherein, the mass content of polysulfones is 15%, the content of acrylonitrile-maleic anhydride
For 5%, the content of zinc oxide is 3%, and polyvinyl pyrrolidone content is 8%, and the content of 1-METHYLPYRROLIDONE is 69%.Control
Room temperature processed is 30 DEG C, and humidity is 70%, regard the casting solution prepared as spinning solution, 70% acetone and the mixing of 30% deionized water
Thing injects core passageway.The rate of extrusion of core liquid is 20 ml/mins, and the rate of extrusion of casting solution is 18 ml/mins.By
5s airspace, into (30 DEG C) solidifications of coagulating bath, forms double-layer hollow fiber film, is collected by up- coiler.Prepare
Hollow-fibre membrane immersion in deionized water, change a water per 4h, change after 3 times and characterization test is carried out to film.Prepare
0.8mol·L-1Tris cushioning liquid 1L, with hydrochloric acid adjust pH to 3, into cushioning liquid add 4g dopamines, by what is prepared
Composite membrane is put into dopamine solution, is put into shaking table concussion coating 10h, afterwards, is taken the film out, be placed again into newly prepare many
Coated again in bar amine aqueous solution, so circulation coating 8 times, concussion cleaning 3 times in deionized water are put into after taking-up.
Obtained composite membrane contact angle is 30 °, and supporting layer thickness is 250 μm, and separating layer thickness is 0.1 μm, dopamine
The thickness of layer is 400nm.At 0.5MPa and 25 DEG C, pure water flux 9Lm is determined with ultrafiltration apparatus-2·h-1, PEG retentions point
Son amount is 600Da, using 100mgL-1Directly red/NaCl salting liquids filtering, salt ion can pass through, to direct red
Rejection is 98%.
Embodiment 5
This method prepares a kind of hydrophilic polyethersulfone dye desalination membrane material.By molecular weight for 200Da polyethylene glycol, point
Son amount is dissolved in acetone for 1,000Da polyether sulfone, acrylonitrile-maleic anhydride and lithium chloride nano particle, is well mixed
Casting solution raw material is configured to, wherein, the mass content of polyethylene glycol is 15%, and the mass content of polyether sulfone is 15%, acrylonitrile-
The content of maleic anhydride is 3%, and the content of lithium chloride nano particle is 2%, and the mass content of acetone is 63%.Control room
Temperature is 25 DEG C, and humidity is 40%, regard the casting solution prepared as spinning solution, 60% acetone and 40% deionized water mixture note
Enter core passageway.The rate of extrusion of core liquid is 15 ml/mins, and the rate of extrusion of casting solution is 15 ml/mins.By 8s's
Airspace, into (50 DEG C) solidifications of coagulating bath, forms double-layer hollow fiber film, is collected by up- coiler.In preparing
Hollow fiber film is soaked in deionized water, and a water is changed per 4h, is changed after 3 times and is carried out characterization test to film.Prepare 0.01molL-1
Tris cushioning liquid 1L, with hydrochloric acid adjust pH to 4, into cushioning liquid add 3g dopamines, the composite membrane prepared is put into
In dopamine solution, shaking table concussion coating 20h is put into, afterwards, takes the film out, is placed again into the dopamine solution newly prepared
Coat again, so circulation coating 7 times, concussion cleaning 3 times in deionized water are put into after taking-up.
Obtained composite membrane contact angle is 30 °, and supporting layer thickness is 250 μm, and separating layer thickness is 0.1 μm, dopamine
The thickness of layer is 350nm.At 0.5MPa and 25 DEG C, pure water flux 12Lm is determined with ultrafiltration apparatus-2·h-1, PEG retentions point
Son amount is 700Da, using 100mgL-1Directly red/NaCl salting liquids filtering, salt ion can pass through, to direct red
Rejection is 96%.
Embodiment 6
This method prepares a kind of hydrophily polyarylsulfone (PAS) dye desalination membrane material.By molecular weight for 1,000Da polyether sulfone, point
Son amount is dissolved in N- methyl pyrroles for 6,000Da polyethylene glycol, inorganic nano Titanium particles, acrylonitrile-maleic anhydride
Pyrrolidone, it is well mixed to be configured to casting solution raw material, wherein, the mass content of zinc oxide is 0.1%, the mass content of polyether sulfone
For 15%, the content of acrylonitrile-maleic anhydride is 0.1%, and the content of polyethylene glycol is 0.1%, N, N- dimethyl formyls
The mass content of amine is 84.7%.It is 25 DEG C to control room temperature, and humidity is 40%, by preparation liquid equably on a glass, is adjusted
The height for saving scraper is 150 μm, and knifing speed is 20mmin-1.It is put into and fills after film stops 8s in atmosphere after having scraped
(25 DEG C) carry out rinsing processing after film idiosome film-forming and after departing from glass plate in the coagulating bath of ionized water, are changed once per 4h
Water, changes after 3 times and carries out characterization test to film.Prepare 0.7molL-1Tris cushioning liquid 1L, with hydrochloric acid adjust pH to 5, Xiang Huan
Addition 5g dopamines in solution are rushed, the composite membrane prepared is put into dopamine solution, shaking table concussion coating 24h is put into, it
Afterwards, take the film out, be placed again into the dopamine solution newly prepared and coat again, so circulation coating 6 times, be put into after taking-up
Concussion cleaning 3 times in deionized water.
Obtained composite membrane contact angle is 26 °, and supporting layer thickness is 150 μm, and separating layer thickness is 0.1 μm, dopamine
The thickness of layer is 300nm.At 0.5MPa and 25 DEG C, pure water flux 13Lm is determined with ultrafiltration apparatus-2·h-1, PEG retentions point
Son amount is 850Da, using 100mgL-1Direct red/MgCl2Salting liquid is filtered, and salt ion can pass through, to direct red
Rejection is 96%.
Embodiment 7
This method prepares a kind of hydrophily polyarylsulfone (PAS) dye desalination membrane material.It is 7 by inorganic oxide zinc particles, molecular weight,
700Da polyarylsulfone (PAS), acrylonitrile-maleic anhydride and molecular mass for 6,000 polyethylene glycol, be dissolved in acetone, mix
Casting solution raw material uniformly is configured to, wherein, the mass content of zinc oxide particles is 5%, and the mass content of polyarylsulfone (PAS) is 25%, third
The content of alkene nitrile-maleic anhydride is 5%, and the content of polyethylene glycol is 15%, the mass content of DMF
For 50%.It is 25 DEG C to control room temperature, and humidity is 40%, and using the casting solution prepared as spinning solution, 50% acetone and 50% is gone
Ion aqueous mixtures inject core passageway.The rate of extrusion of core liquid is 10 ml/mins, and the rate of extrusion of casting solution is 10 millis
Liter/min.By 12s airspace, into (50 DEG C) solidifications of coagulating bath, double-layer hollow fiber film is formed, is entered by up- coiler
Row is collected.The hollow-fibre membrane immersion prepared in deionized water, a water is changed per 4h, is changed after 3 times and is carried out sign survey to film
Examination.Prepare 0.9molL-1Tris cushioning liquid 1L, with hydrochloric acid adjust pH to 6, into cushioning liquid add 3g dopamines, will make
The composite membrane got ready is put into dopamine solution, is put into shaking table concussion coating 10h, afterwards, is taken the film out, be placed again into new preparation
Coated again in good dopamine solution, so circulation coating 5 times, concussion cleaning 3 times in deionized water are put into after taking-up.
Obtained composite membrane contact angle is 30 °, and supporting layer thickness is 250 μm, and separating layer thickness is 0.1 μm, dopamine
The thickness of layer is 250nm.At 0.5MPa and 25 DEG C, pure water flux 14Lm is determined with ultrafiltration apparatus-2·h-1, PEG retentions point
Son amount is 800Da, using 100mgL-1Directly red/NaCl salting liquids filtering, salt ion can pass through, to direct red
Rejection is 95%.
Embodiment 8
This method prepares a kind of hydrophilic polyethersulfone dye desalination membrane material.It is 1 by zirconium oxide nano-particle, molecular weight,
000Da PPSU, acrylonitrile-maleic anhydride and molecular weight is dissolved in acetone for 10,000Da polyethylene glycol, mixes
Casting solution raw material uniformly is configured to, wherein, the mass content of polyvinylpyrrolidone is 10%, and the mass content of PPSU is
20%, zirconium oxide nano-particle content is 1%, and the mass content of DMF is 69%.It is 25 DEG C to control room temperature,
Humidity is 40%, is led to the casting solution prepared as spinning solution, 70% acetone and 30% deionized water mixture injection inner core
Road.The rate of extrusion of core liquid is 1 ml/min, and the rate of extrusion of casting solution is 1 ml/min.By 3s airspace,
Into (50 DEG C) solidifications of coagulating bath, double-layer hollow fiber film is formed, is collected by up- coiler.The hollow-fibre membrane leaching prepared
Bubble in deionized water, a water is changed per 4h, is changed after 3 times and is carried out characterization test to film.Prepare 0.01molL-1Tris buffering
Solution 1L, pH to 8 is adjusted with hydrochloric acid, and 3g dopamines are added into cushioning liquid, the composite membrane prepared is put into dopamine solution
In, shaking table concussion coating 18h is put into, afterwards, is taken the film out, is placed again into the dopamine solution newly prepared and coats again,
So circulation coating 4 times, is put into concussion cleaning 3 times in deionized water after taking-up.
Obtained composite membrane contact angle is 30 °, and supporting layer thickness is 250 μm, and separating layer thickness is 0.1 μm, dopamine
The thickness of layer is 200nm.At 0.5MPa and 25 DEG C, pure water flux 15Lm is determined with ultrafiltration apparatus-2·h-1, PEG retentions point
Son amount is 850Da, using 100mgL-1Directly red/NaCl salting liquids filtering, salt ion can pass through, to direct red
Rejection is 92%.
Claims (9)
1. a kind of hydrophilic polysulfone film, it is characterised in that by polysulfones-like polymer, acrylonitrile-maleic anhydride polymer group
Into composite membrane and coating composite membrane on DOPA amine layer composition, wherein the supporting layer thickness of composite membrane be 10~300 μm, separation
Thickness degree is 0.1~0.5 μm, and the thickness of DOPA amine layer is about 50~500nm, the film of modified obtained hydrophilic polysulfone film
Molecular cut off is 500~4,000Da.
2. hydrophilic polysulfone film according to claim 1, it is characterised in that described polysulfones-like polymer is polysulfones, gathered
Ether sulfone, PPSU or polyarylsulfone (PAS), wherein polysulfones molecular weight are 1,700~3,500Da, and polyether sulfone molecular weight is 1,000~6,
020Da, PPSU molecular weight is 3,000~5,000Da, and polyarylsulfone (PAS) molecular weight is 1,000~7,700Da.
3. a kind of method of the hydrophilic polysulfone film prepared as described in right 1, it is comprised the following steps that：
(A) preparation liquid is prepared
Polysulfones-like polymer, organic additive, inorganic additive and acrylonitrile-maleic anhydride polymer are dissolved in organic molten
In agent, it is well mixed and prepares casting solution raw material, wherein, the mass content of polysulfones-like polymer is 15~25%, organic additive
Mass content be that the mass content of 0.1~15%, inorganic additive is 0.1~5%, acrylonitrile-maleic anhydride polymerization
Thing content 0.1~5%；Organic solvent 50%~84.7%；
(B) preparation of film
The preparation of film is divided into the preparation of Flat Membrane or hollow-fibre membrane：
The preparation method of Flat Membrane：Temperature be 15~30 DEG C, humidity be 30~70% under, the film that step (A) is prepared
On a glass, the thickness of regulation scraper is 10~300 μm to liquid, and knifing speed is 5~50mmin-1, when stopping in air
Between 3~20s, the film scraped is put into coagulating bath together with glass plate, control coagulation bath temperature be 10~50 DEG C, handled through rinsing
Afterwards, polysulfones composite membrane is obtained；
The preparation method of hollow-fibre membrane：Temperature be 15~30 DEG C, humidity be 30~70% under, step (A) is prepared
Spinning solution and core liquid are injected binary channels spinning head by supporting layer casting solution simultaneously as spinning solution, and its SMIS liquid injection inner core leads to
Road, spinning solution injection outer layer channel, extrusion prepares 3~20s of residence time in hollow-fibre membrane idiosome, air, will prepared
Doughnut idiosome be put into coagulating bath, control coagulation bath temperature be 10~50 DEG C；
(C) dopamine repeatedly coats polysulfones composite membrane
The preparation of Tris-HCl buffer solutions：Prepare 0.01~1molL-1Tris solution, with hydrochloric acid adjust pH to 1~9, Ran Houxiang
Dopamine is added in buffer solution, dopamine concentration is 1~6gL-1, the composite membrane prepared is put into dopamine solution, put
Enter shaking table concussion 6~24h of coating, afterwards, take the film out, or be put into the dopamine solution newly prepared and coat again, obtain
Hydrophilic polysulfone film.
4. method according to claim 3, it is characterised in that described organic additive molecular weight is 10,000~360,
000Da polyvinylpyrrolidone or molecular weight is one kind or any several group in 200~10,000Da polyethylene glycol
Close.
5. method according to claim 3, it is characterised in that described inorganic additive is titanium oxide, aluminum oxide, oxidation
Zinc, zirconium oxide or lithium chloride.
6. method according to claim 3, it is characterised in that the organic solvent in step A is DMF,
DMAC N,N' dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO) or acetone.
7. method according to claim 3, it is characterised in that the rate of extrusion of the preparation process SMIS liquid of hollow-fibre membrane
For 1~20 ml/min, the speed of spinning solution extrusion is 1~18 ml/min.
8. method according to claim 3, be characterised by the core liquid described in the preparation process of hollow-fibre membrane for go from
The mixture of sub- water and solvent；Wherein solvent is N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, N- crassitudes
Ketone, dimethyl sulfoxide (DMSO) or acetone；The content of core liquid reclaimed water accounts for 20~50%.
9. method according to claim 3, it is 1~10 time to be characterised by the number of times coated again in step C.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107715708A (en) * | 2017-09-26 | 2018-02-23 | 河海大学 | Preparation method and its renovation process for the renewable polyelectrolyte film of positive infiltration technology |
| FR3078267A1 (en) * | 2018-02-27 | 2019-08-30 | Li Shengmin | ULTRAFILTRATION MEMBRANE AND METHOD FOR PREPARING THE SAME |
| CN112044291A (en) * | 2020-09-23 | 2020-12-08 | 天津工业大学 | Compact separation membrane |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935341A (en) * | 2006-09-07 | 2007-03-28 | 东华大学 | Polysulfone and polyethy lene base polymer blend membrane, and its preparing and use |
| CN101229489A (en) * | 2007-10-26 | 2008-07-30 | 吴特殊 | Film making liquid for polyvinyl chloride hydrophilicity alloy separating film and preparing method thereof |
| CN105854650A (en) * | 2016-06-17 | 2016-08-17 | 安庆市天虹新型材料科技有限公司 | Anti-fouling high-throughput polysulfone composite membrane |
-
2017
- 2017-03-07 CN CN201710130243.0A patent/CN106943899B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935341A (en) * | 2006-09-07 | 2007-03-28 | 东华大学 | Polysulfone and polyethy lene base polymer blend membrane, and its preparing and use |
| CN101229489A (en) * | 2007-10-26 | 2008-07-30 | 吴特殊 | Film making liquid for polyvinyl chloride hydrophilicity alloy separating film and preparing method thereof |
| CN105854650A (en) * | 2016-06-17 | 2016-08-17 | 安庆市天虹新型材料科技有限公司 | Anti-fouling high-throughput polysulfone composite membrane |
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|---|---|---|---|---|
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| CN107715708A (en) * | 2017-09-26 | 2018-02-23 | 河海大学 | Preparation method and its renovation process for the renewable polyelectrolyte film of positive infiltration technology |
| FR3078267A1 (en) * | 2018-02-27 | 2019-08-30 | Li Shengmin | ULTRAFILTRATION MEMBRANE AND METHOD FOR PREPARING THE SAME |
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| CN112675820A (en) * | 2020-11-02 | 2021-04-20 | 佛山市博新生物科技有限公司 | Blood purification membrane and preparation method and application thereof |
| CN113185426A (en) * | 2021-04-24 | 2021-07-30 | 浙江锦华新材料股份有限公司 | Refining method of methoxylamine hydrochloride |
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