CN102728249B - Polymer hollow fiber porous membrane and preparation method thereof - Google Patents
Polymer hollow fiber porous membrane and preparation method thereof Download PDFInfo
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- CN102728249B CN102728249B CN201210255623.4A CN201210255623A CN102728249B CN 102728249 B CN102728249 B CN 102728249B CN 201210255623 A CN201210255623 A CN 201210255623A CN 102728249 B CN102728249 B CN 102728249B
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Abstract
The invention discloses a polymer hollow fiber porous membrane and a preparation method of the polymer hollow fiber porous membrane. The membrane comprises the following raw materials in percentage by weight: 20-32% of membrane forming polymer, 38-60% water-soluble additive, 8-15% inorganic particles, and 8-15% organic liquid, wherein the membrane forming polymer is an ethylene-vinyl acetate copolymer, or a polymer blend of ethylene-vinyl acetate copolymer and polyurethane, and the polyurethane in the blend is 1-35% of total mass of the membrane forming polymer; the mass content of the vinyl acetate in the ethylene-vinyl acetate copolymer is 28%, and the melt index is 25g/10min; and the polyurethane is at fiber grade, and the mass ratio of hard segment to soft segment is 2:3. The preparation method comprises the following processes of preparing the membrane forming polymer blend; preparing a primary hollow membrane; conducting aftertreatment to the primary hollow membrane, thus obtaining the hollow membrane.
Description
Technical field
The present invention relates to membrane technology field, be specially a kind of polymer hollow fiber multihole film and preparation method thereof.
Background technology
Over nearly 30 years, thermoplastic elastomer (TPE) is described as third generation rubber and has obtained very swift and violent development all over the world.It is the block polymer that a kind of soft chain segment and hard segment alternately connect and compose, and under room temperature, has caoutchouc elasticity, can plasticizing forming under high temperature, both there is the mechanical property and the serviceability that are similar to rubber, and can process and reclaim according to thermoplastic again.In recent years, due to membrane separation technique there is normal-temperature operation, without phase transformation, without chemical change, selectively good, strong adaptability, low power consumption and other advantages, all enjoy high praise in fields such as food processing, desalinization, pure water, ultra-pure water preparation, medicine, biology, environmental protection.As the core of membrane separation technique---performance of film and preparation method thereof has received many-sided concern.Film is classified according to preparing material, can be divided into two kinds of organic film and inoranic membranes, because inoranic membrane is expensive, easily crisp, it is extensive that its range of application can not show a candle to polymer film.But now on market, existing polymer film is normal film material, its microcellular structure, as aperture and micropore number can not change along with environmental condition.Under laboratory condition, make the smart membrane material with environment controllability.Fan Hao army of Sichuan University etc. has made Thermo-sensitive polyurethane film, and uses it for (polymer material science and engineering, 2009 years 25 volumes, the 89-95 page of separating of sodium chloride, glycine and collagen; Desalination, 249 volumes in 2009,843-849 page), Zhou Hu etc. are taking Thermo-sensitive polyurethane material as basement membrane, utilize surface grafting technology to arrive membrane surface with the acrylic acid initiation grafting of the responsive functional group of pH, successfully prepare a kind of polyurethane film (chemical propellant and macromolecular material, 9 volumes in 2011,81-85 page) to temperature, pH Dual Sensitive.Patent documentation CN1594405A, CN1673271A and CN101879418A have all announced the preparation method of pH sensitive membrane.Applicant, once taking polyurethane as masking matrix material, by melt spinning-pulling method, utilizes interface hole creating technology, has made the polyurethane series hollow-fibre membrane (CN101322922A, CN1883778A) with pressure-responsive function.Ethylene-vinyl acetate copolymer (being called for short EVA) is as a kind of thermoplastic elastomer (TPE), be normally used for the dense film for the preparation of fields such as gas separation, infiltration evaporations in masking field, about EVA be there is not yet for the preparation of the research report of hollow fiber porous film, main cause is, the glass transition temperature of EVA is generally lower than room temperature, and self-supporting is poor, and pure EVA pore-forming difficulty, after film forming, general dense non-porous, is unfit to do perforated membrane.
Summary of the invention
For the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that a kind of polymer hollow fiber multihole film and preparation method thereof is provided.This hollow fiber porous film has adopted the blend of ethylene-vinyl acetate copolymer and polyurethane, and membrane aperture is distributed within the scope of micro-filtration, and supportive is good, and test pressure is had to memory function, and repeatedly the rear recoverability of test is good; This preparation method's technique is simple, and easily drilling, is convenient to actual production.
The technical scheme that the present invention solves described porous membrane problem is: design a kind of polymer hollow fiber multihole film, it is characterized in that this perforated membrane mass percent consists of:
Film forming polymer 20-32%;
Water-soluble additive 38-60%;
Inorganic particulate 8-15%;
Organic liquid 8-15%; Each component sum is 100%,
Described film forming polymer is the copolymer of ethene-vinyl acetate, or the copolymer of ethene-vinyl acetate and the blend of polyurethane, and in blend, polyurethane accounts for the 1-35% of film forming polymer gross mass; In described ethylene-vinyl acetate copolymer, the mass content of vinyl acetate is 28%, and melt index is 25g/10min; Described polyurethane is fibre-grade, and hard section is 2: 3 with soft section of mass ratio;
Described water-soluble additive is the mixture of water-soluble polymer and any proportioning of water-soluble inorganic salt, and wherein, described water-soluble polymer is the one in polyethylene glycol, polyethylene glycol oxide or polyvinylpyrrolidone; Described inorganic salts are at least one in lithium chloride, potassium chloride, sodium chloride and calcium chloride; Described inorganic particulate is the SiO of average grain diameter 0.01-10 μ m
2and CaCO
3in the mixture of one or both arbitrary proportions; Described organic liquid is the good solvent of polyurethane, comprises dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO).
The technical scheme that the present invention solves described preparation method's technical problem is: the preparation method who designs a kind of polymer hollow fiber multihole film, this preparation method adopts perforated membrane mass percent composition of the present invention and following melt spinning-stretching pore-forming technique, comprising:
(1). according to described ratio, first described inorganic particulate is mixed with organic liquid, then add water-soluble additive, mix, then add described film forming polymer, mix, make the blend of film forming polymer;
(2). gained blend is evenly fed to double screw extruder, at 130-145 ° of C temperature, enter hollow-fiber module through measuring pump squeezing out quantitative, component internal passes into nitrogen or air, the center cavity that forms hollow fiber porous film, makes nascent hollow fiber porous film;
(3). the nascent hollow fiber porous film of gained, after 5-15cm air bath, enters first water-bath, and bath temperature is 10-55 DEG C, and spinneret draft ratio is 2-4 times; After coiling, in the time of tunica fibrosa completion of cure, at once carry out after-drawing, after-drawing multiple is 1.5-4 times; Then in second water-bath, carry out fixed length thermal finalization, second bath temperature is 40-60 DEG C, and fixed length heat-setting time is 40-80min; Finally obtained hollow fiber porous film is put into normal-temperature water, continue extraction and wash 48h, obtain described polymer hollow fiber multihole film.
Compared with prior art, polymer hollow fiber multihole film of the present invention designs and has adopted ethylene-vinyl acetate copolymer or its mixture in compositing formula, be aided with water-soluble additive, organic liquid and inorganic particulate, can wash drilling, stretching pore, have the multiple microcellular structure of stripping hole and interface micropore simultaneously, the pore-size distribution of micropore is within the scope of micro-filtration, water permeability is good, and supportive is good, and test pressure is had to memory function, repeatedly after test, recoverability is good.Melt spinning-stretching technique that preparation method of the present invention has adopted, and water-soluble additive and organic liquid in compositing formula, are designed, in preparation process, can remove through simple washing, and the existence of inorganic particulate in formula, in conjunction with the after-drawing technique in spinning process, can, at polymer/inorganic particle interface formation interface micropore, further improve the porosity of film, preparation method is simple to operate, is convenient to production application.
Brief description of the drawings
Fig. 1 is the pressure response curve schematic diagram of a kind of embodiment of polymer hollow fiber multihole film of the present invention (embodiment 1).
Fig. 2 is the pressure response curve schematic diagram of the another kind of embodiment of polymer hollow fiber multihole film of the present invention (embodiment 2).
Detailed description of the invention
Further narrate the present invention below in conjunction with embodiment and accompanying drawing:
Polymer hollow fiber multihole film (hereinafter to be referred as hollow membrane) the mass percent composition of the present invention's design is:
Film forming polymer 20-32%;
Water-soluble additive 38-60%;
Inorganic particulate 8-15%;
Organic liquid 8-15%; Each component sum is 100%,
Described film forming polymer is ethylene-vinyl acetate copolymer, or the blend of ethylene-vinyl acetate copolymer and polyurethane, and in blend, polyurethane accounts for the 1-35% of film forming polymer gross mass, but preferred proportion is 20-30%; In described ethylene-vinyl acetate copolymer, the mass content of vinyl acetate is 28%, and melt index is 25g/10min; Described polyurethane is fibre-grade, and hard section is 2:3 with soft section of mass ratio.
Water-soluble additive of the present invention is the mixture of water-soluble polymer and any proportioning of water-soluble inorganic salt.The selection of water-soluble additive is according to being: 1, be easy to dissolve in water, can in the process of washing, remove rapidly quenching; , can there is not chemical change in 2, stable in properties within the scope of spinning temperature; 3, spinning process can not affect that it is water-soluble.Accordingly, in water-soluble additive of the present invention, water-soluble polymer is the one in polyethylene glycol, polyethylene glycol oxide and polyvinylpyrrolidone; Described inorganic salts are at least one in lithium chloride, potassium chloride, sodium chloride and calcium chloride.Experimental study shows, in compositing formula of the present invention, within the specific limits, water-soluble additive is in the situation that being evenly distributed, and content is higher, after washing through quenching, the water flux that makes film is larger, but the simultaneously homogeneity phase strain differential of mechanical performance, supportive and fenestra, therefore in film forming compositing formula of the present invention, the gross mass of film forming polymer should account for film forming system gross mass more than 20% and the gross mass of water-soluble additive should account for the more than 38% of film forming system gross mass.In addition, the average molecular mass of water-soluble polymer changes also has considerable influence to the pore structure of gained hollow fiber porous film, if average molecular mass is lower, spinning process medium viscosity is lower, be easy to be distributed in hollow fiber porous film surface, reduce the permeability between fenestra, cause membrane flux to decline, so the polyethylene glycol oxide of the polyethylene glycol of the preferred average molecular mass 6,000-20,000 of water-soluble polymer, average molecular mass 50,000-100,000 or the polyvinylpyrrolidone of average molecular mass 40,000; For the consideration of viscosity, in water-soluble additive, water-soluble inorganic salt should account for the 15-30% of water-soluble additive gross mass equally.
The selection of inorganic particulate of the present invention is according to being: 1, particle size range, within the scope of 0.01-10 μ m, can form interface with film forming polymer, and is dispersed in uniformly in film forming system; 2,, after inorganic particulate adds, do not affect the spinning processing performance of film forming system; 3, after inorganic particulate adds, to the hollow fiber porous film of final molding without physical damnification and chemical damage.Accordingly, inorganic particulate of the present invention is chosen as the SiO of average grain diameter 0.01-10 μ m
2and CaCO
3in a kind of mixture of or two kinds of arbitrary proportions;
Organic liquid of the present invention is the good solvent of polyurethane, comprises dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO).
The present invention has designed the preparation method (abbreviation preparation method) of described polymer hollow fiber multihole film simultaneously.This preparation method adopts polymer hollow fiber multihole film quality percentage composition of the present invention (or film forming system) and following melt spinning-stretching pore-forming technique, comprising:
(1). according to described ratio, first described inorganic particulate is mixed with organic liquid, then add water-soluble additive, mix, then add described film forming polymer, mix, make the blend of film forming polymer;
(2). gained blend is evenly fed to double screw extruder, at 130-145 ° of C temperature, enter hollow-fiber module through measuring pump squeezing out quantitative, component internal passes into nitrogen or air, the center cavity that forms hollow fiber porous film, makes nascent hollow fiber porous film;
(3). the nascent hollow fiber porous film of gained, after 5-15cm air bath, enters first water-bath, and bath temperature is 10-55 DEG C, and spinneret draft ratio is 2-4 times; After coiling, in the time of tunica fibrosa completion of cure, at once carry out after-drawing, after-drawing multiple is 1.5-4 times; Then in second water-bath, carry out fixed length thermal finalization, second bath temperature is 40-60 DEG C, and fixed length heat-setting time is 40-80min; Finally obtained hollow fiber porous film is put into normal-temperature water, continue extraction and wash 48h, obtain described polymer hollow fiber multihole film.
Film forming system of the present invention comprises four kinds of components, i.e. film forming polymer, water-soluble additive, inorganic particulate and organic liquid.When carrying out blend in technique and preparing, should first inorganic particulate be mixed according to described ratio with organic liquid, then add in proportion water-soluble additives mixed even, then proportionally add film forming polymer, be the mixture of ethylene-vinyl acetate copolymer or itself and polyurethane, further mix.Can make like this organic liquid fully be adsorbed by inorganic particulate, be conducive to film forming system and mix.
Preparation method of the present invention adopts known melt spinning-stretching pore-forming technique, film forming blend is evenly fed to double screw extruder, at 130-145 DEG C of temperature, enter hollow-fiber module through measuring pump squeezing out quantitative, component internal passes into nitrogen or air, form hollow-fibre membrane center cavity, make nascent hollow fiber porous film.Then the nascent hollow fiber porous film of gained enters first water-bath after 5-15cm air bath, and bath temperature is 10-55 DEG C, and spinneret draft ratio is 2-4 times; After coiling, at once carry out after-drawing in the time of fiber completion of cure, after-drawing multiple is 1.5-4 times; Then in second water-bath, carry out fixed length thermal finalization, second water-bath or fixed length heat setting temperature are that 40-60 DEG C, time are 40-80min.Finally prepared hollow fiber porous film is put into normal-temperature water continuation extraction and washed 48h, obtain described ethylene-vinyl acetate copolymer blend hollow fiber porous film.
The obtained hollow fiber porous film curing rate of the present invention is slower, therefore, in technique, to extend the length of nascent hollow fiber porous film through water-bath with known method, so that after hollow fiber porous film coiling, do not affect the formation of its cavity, and perforated membrane also can not stick together each other, and then carry out after-drawing, after-drawing multiple is 1.5-4 times, preferably after-drawing multiple is 1.5-2.5 times, after-drawing multiple is excessive, can expand the pore-size distribution of hollow fiber porous film, reduces the filtering accuracy of film.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below, but embodiment illustrates the present invention, does not limit the protection domain of the present patent application claim.
Embodiment 1
Taking pure ethylene-vinyl acetate copolymer as film forming polymer, quality percentage composition is 25%; Water-soluble additive quality percentage composition is 51%, the water-soluble polymer polyethylene glycol 20,000 that is 23% comprising quality percentage composition, and the quality percentage composition water-soluble inorganic salt zinc chloride that is 77%; Inorganic particulate quality percentage composition is 12%, is the SiO of 1 μ m by average grain diameter
2and CaCO
3each 50% composition; Organic liquid selects dimethyl sulfoxide (DMSO), quality percentage composition is 12%, by said mixture according to first by inorganic particulate and organic liquid blend, then add water-soluble additives, after finally adding the order of film forming polymer to mix, feeding double screw extruder, at 135 DEG C of temperature, enter hollow-fiber module through measuring pump squeezing out quantitative, component internal passes into air, to form the center cavity of hollow-fibre membrane, make nascent hollow fiber porous film.Then the nascent hollow fiber porous film of gained enters first water-bath after 5cm air bath, and bath temperature is 50 DEG C, and spinneret draft ratio is 4 times; After coiling, in the time of fiber completion of cure, carry out at once after-drawing, after-drawing multiple is 1.5 times; Then in second water-bath, carry out fixed length thermal finalization, second bath temperature is 50 DEG C, and fixed length heat-setting time is 40min.Finally obtained hollow fiber porous film is put into normal-temperature water continuation extraction and washed 48h, make described polymer hollow fiber perforated membrane.
Through inspection, the present embodiment gained hollow fiber porous film is at 0.1MPa and 25 DEG C, and in adopting, to record water flux be 4631L/m to platen press
2h has measured the hollow fiber porous film water flux of 8 circulations with the change curve (referring to Fig. 1) of pressure simultaneously.This curve shows is along with rising or the reduction of pressure, and obtained hollow fiber porous film water flux increases thereupon or reduces, and shows pressure-responsive, and after repeatedly measuring, water flux is along with pressure trend is consistent, better repeatable.
Embodiment 2
Film forming polymer in embodiment 1 is adjusted into the blend of ethylene-vinyl acetate copolymer and polyurethane, wherein polyurethane accounts for 25% of film forming polymer gross mass, spinneret draft ratio is adjusted into 3 times, after-drawing multiple is adjusted into 2 times, fixed length heat-setting time is adjusted into 60min, and when hollow-fibre membrane moulding, hollow component internal passes into nitrogen, other conditions are constant, can make hollow fiber porous film of the present invention.
Through inspection, the present embodiment gained hollow fiber porous film is at 0.1MPa and 25 DEG C, and in adopting, to record water flux be 2716L/m to platen press
2h has measured the hollow fiber porous film water flux of 8 circulations with the change curve (referring to Fig. 2) of pressure simultaneously.This curve shows is along with rising or the reduction of pressure, and obtained hollow fiber porous film water flux increases thereupon or reduces, and shows pressure-responsive, and after repeatedly measuring, water flux is along with pressure trend is consistent, better repeatable.
Embodiment 3
Water-soluble polymer in water-soluble additive in embodiment 2 is adjusted into polyethylene glycol 6,000, water-soluble inorganic salt is adjusted into the mixture of zinc chloride and calcium chloride, wherein zinc chloride and calcium chloride account for respectively 70% and 30% of water-soluble inorganic salt gross mass, other conditions are constant, can make described hollow fiber porous film.
Through inspection, the present embodiment gained hollow fiber porous film is at 0.1MPa and 25 DEG C, and in adopting, to record water flux be 1842L/m to platen press
2h.
Embodiment 4
The content that film forming polymer in embodiment 2 is accounted for to gross mass is adjusted into 30%, and wherein the content of polyurethane is adjusted into 15%; Water-soluble additive accounts for 42% of gross mass, comprising the water-soluble polymer polyethylene glycol oxide 50,000,40% water-soluble inorganic salt sodium chloride and 40% the water-soluble inorganic salt zinc chloride that account for water-soluble additive gross mass 20%; Inorganic particulate accounts for 14% of gross mass, is the SiO of 1 μ m comprising average grain diameter
2and CaCO
3respectively account for inorganic particulate gross mass 60%, 40%; Organic liquid selects dimethyl formamide, and quality percentage composition is 14%, and other conditions are constant, can make described hollow fiber porous film.
Through inspection, the present embodiment gained hollow fiber porous film is at 0.1MPa and 25 DEG C, and in adopting, to record water flux be 1497L/m to platen press
2h.
Embodiment 5
By in embodiment 4, inorganic particulate is replaced by the SiO that average grain diameter is 0.5 μ m
2and CaCO
3, all the other conditions are constant, can make described hollow fiber porous film.
Through inspection, the present embodiment gained hollow fiber porous film is at 0.1MPa and 25 DEG C, and in adopting, to record water flux be 3017L/m to platen press
2h.
Embodiment 6
By in embodiment 4, the content that film forming polymer accounts for gross mass is adjusted into 22%, and wherein the content of polyurethane is adjusted into 30%; Water-soluble additive accounts for 56% of gross mass, comprising the water-soluble polymer polyethylene glycol oxide 50,000,40% water-soluble inorganic salt sodium chloride and 40% the water-soluble inorganic salt zinc chloride that account for water-soluble additive gross mass 20%; Inorganic particulate accounts for 11% of gross mass, is the SiO of 1 μ m comprising average grain diameter
2and CaCO
3respectively account for inorganic particulate gross mass 60%, 40%; Organic liquid selects dimethylacetylamide, and quality percentage composition is 11%, and other conditions are constant, can make described hollow fiber porous film.
Through inspection, the hollow fiber porous film of the present embodiment gained is at 0.1MPa and 25 DEG C, and in adopting, to record water flux be 3204L/m to platen press
2h.
Claims (6)
1. a polymer hollow fiber multihole film, is characterized in that the mass percent composition of this hollow fiber porous film is:
Film forming polymer 20-32%;
Water-soluble additive 38-60%;
Inorganic particulate 8-15%;
Organic liquid 8-15%; Each component sum is 100%,
Described film forming polymer is the copolymer of ethene-vinyl acetate, or the copolymer of ethene-vinyl acetate and the blend of polyurethane, and in blend, polyurethane accounts for the 1-35% of film forming polymer gross mass; In described ethylene-vinyl acetate copolymer, the mass content of vinyl acetate is 28%, and melt index is 25g/10min; Described polyurethane is fibre-grade, and hard section is 2: 3 with soft section of mass ratio;
Described water-soluble additive is the mixture of water-soluble polymer and any proportioning of water-soluble inorganic salt, and wherein, described water-soluble polymer is the one in polyethylene glycol, polyethylene glycol oxide or polyvinylpyrrolidone; Described inorganic salts are at least one in lithium chloride, potassium chloride, sodium chloride and calcium chloride; Described inorganic particulate is the SiO of average grain diameter 0.01-10 μ m
2and CaCO
3in the mixture of one or both arbitrary proportions; Described organic liquid is the good solvent of polyurethane, comprises dimethyl formamide, dimethylacetylamide or dimethyl sulfoxide (DMSO).
2. polymer hollow fiber multihole film according to claim 1, is characterized in that described water-soluble polymer is polyethylene glycol, the polyethylene glycol oxide of average molecular mass 50,000-100,000 or the polyvinylpyrrolidone of average molecular mass 40,000 of average molecular mass 6,000-20,000.
3. polymer hollow fiber multihole film according to claim 1, is characterized in that the water-soluble inorganic salt in described water-soluble additive accounts for the 15-30% of water-soluble additive gross mass.
4. polymer hollow fiber multihole film according to claim 1, is characterized in that described film forming polymer is the blend of ethylene-vinyl acetate copolymer and polyurethane, and in blend, polyurethane accounts for the 20-30% of film forming polymer gross mass.
5. a preparation method for polymer hollow fiber multihole film described in claim 1-4 any one, is characterized in that this preparation method adopts melt spinning-stretching pore-forming technique, comprising:
(1). according to described ratio, first described inorganic particulate is mixed with organic liquid, then add water-soluble additive, mix, then add described film forming polymer, mix, make the blend of film forming polymer;
(2). gained blend is evenly fed to double screw extruder, at 130-145 ° of C temperature, enter hollow-fiber module through measuring pump squeezing out quantitative, component internal passes into nitrogen or air, the center cavity that forms hollow fiber porous film, makes nascent hollow fiber porous film;
(3). the nascent hollow fiber porous film of gained, after 5-15cm air bath, enters first water-bath, and bath temperature is 10-55 DEG C, and spinneret draft ratio is 2-4 times; After coiling, in the time of tunica fibrosa completion of cure, at once carry out after-drawing, after-drawing multiple is 1.5-4 times; Then in second water-bath, carry out fixed length thermal finalization, second bath temperature is 40-60 DEG C, and fixed length heat-setting time is 40-80min; Finally obtained hollow fiber porous film is put into normal-temperature water, continue extraction and wash 48h, obtain described polymer hollow fiber multihole film.
6. the preparation method of polymer hollow fiber multihole film according to claim 5, it is characterized in that described after-drawing multiple be 1.5-2.5 doubly.
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| CN103752179A (en) * | 2014-01-09 | 2014-04-30 | 天津工业大学 | Preparation method of hydrophobic hollow fiber membrane |
| CN108554204A (en) * | 2018-01-08 | 2018-09-21 | 天津工业大学 | A kind of preparation method of polyvinyl chloride hollow fiber perforated membrane |
| CN109065816A (en) * | 2018-08-14 | 2018-12-21 | 湘潭大学 | A kind of polyurethane-nano material composite diaphragm and Preparation method and use |
| CN109457306B (en) * | 2018-10-25 | 2021-03-30 | 浙江理工大学 | Preparation method of bidirectional shape memory fiber |
| CN115677412B (en) * | 2022-11-18 | 2024-02-23 | 西安德农生物科技有限公司 | Fertilizer capable of protecting crop fruit surfaces and preparation method thereof |
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|---|---|---|---|---|
| CN1883778A (en) * | 2006-05-26 | 2006-12-27 | 天津工业大学 | Polyurethane blended hollow fiber membrane and method for preparing same |
| CN101322922A (en) * | 2008-07-21 | 2008-12-17 | 天津工业大学 | Hollow fiber film and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1883778A (en) * | 2006-05-26 | 2006-12-27 | 天津工业大学 | Polyurethane blended hollow fiber membrane and method for preparing same |
| CN101322922A (en) * | 2008-07-21 | 2008-12-17 | 天津工业大学 | Hollow fiber film and method for producing the same |
Non-Patent Citations (2)
| Title |
|---|
| 中空纤维膜研究进展;张亨;《化工新型材料》;20030430;第31卷(第4期);第7页 * |
| 张亨.中空纤维膜研究进展.《化工新型材料》.2003,第31卷(第4期), |
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