CN102000515B - Thermoplastic polyurethane hollow fiber membrane and preparation method thereof - Google Patents
Thermoplastic polyurethane hollow fiber membrane and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a thermoplastic polyurethane hollow fiber membrane and a preparation method thereof. The hollow fiber membrane is made of polyurethane and prepared by adopting a thermally induced phase separation process. The preparation method comprises the following steps of: mixing thermoplastic polyurethane, thinner, inorganic pore-forming agent and antioxidant uniformly by using a high-speed stirrer, melting and extruding the mixture into granules by using a double-screw extruder, then melting and extruding the granules into hollow fibers by using a single-screw extruder, performing cooling molding, and finally extracting the thinner and the inorganic pore-forming agent in the hollow fibers. The prepared thermoplastic polyurethane hollow fiber membrane has the advantages of high flux, tensile strength and compressive strength, good flexibility of membrane silks, high elongation of the membrane silks at break, good chemical tolerance, permanent hydrophilic property, dry storage and the like. The fiber membrane can be applied to filtration of household and commercial drinking water, filtration and purification of brewed wine, food and medicaments, municipal tap water and sewage treatment, industrial sewage treatment, sea water desalinization pretreatment and the like.
Description
Technical field
The present invention relates to a kind of thermoplastic polyurethane hollow fiber membrane and preparation method thereof-thermally induced phase separation.
Background technology
In recent years industrial develop rapidly, but cause simultaneously the pollution of environment also more and more serious, waste gas, waste liquid, the solid slag of factory's discharging are very large to the pollution of surrounding environment, and the waste liquid that wherein produces is very serious to the pollution of water, and serious threat is to human living environment.Membrane separation technique develops over year rapidly at nearly twenty or thirty, compare with traditional separation method, membrane separating method has the advantages such as efficiency is low, technique simple, environmentally safe, membrane separation technique is widely used in the wastewater treatment of the industry such as chemical industry, food, medicine, electronics, electric power, municipal tap water and sewage disposal, family expenses and commercial Drinking Water Filtration are processed, the aspects such as desalinization.For the manufacture of the material of diffusion barrier, from cellulose acetate, develop into polyethylene, polypropylene, polyvinyl chloride, polyacrylonitrile, polysulfones, Kynoar, polyether sulfone etc.The film manufacturing process has phase separation, melt spinning-stretching hole forming method and thermally induced phase separation.
Plastic polyurethane also is polyurethane elastomer, has not only had the characteristic of plastics but also has had the characteristic of rubber concurrently, has the incomparable good toughness of other plastic material, shock-resistant, and good springiness, elongation at break are high, and elongation at break is more than 500%; Have simultaneously the incomparable high strength of other elastomeric material, tensile strength can reach more than the 25MPa; Have the characteristics such as wear-resisting, cold-resistant, oil resistant, water-fast, ageing-resistant, weatherability, ozone resistance is good, chemical proofing is good.Thermoplastic polyurethane has good processing characteristics, can extrude as the plastic material, the technological forming such as injection.The cost ratio polyether sulfone of thermoplastic polyurethane, Kynoar are cheap, are fit to very much the preparation hollow-fibre membrane.China Patent Publication No. CN 101306329A has introduced a kind of preparation method of polyurethane hollow fiber filter membrane, obtain polyurethane prepolymer after polyalcohol, isocyanates and pre-polymerization additive stirred, generate the polyurethane film-forming glue to wherein adding solvent, chain extender and additive again, use simultaneously setting medium in the preparation of solvent and additive, prepare polyurethane hollow fiber filter membrane with dried-wet spinning silk technique.The method needs polyurethane preformed polymer, and processing step is complicated, and doing of adopting-wet method is phase separation method technique, and the doughnut film strength of preparation is relatively poor.China Patent No. ZL200610013868.0 has introduced a kind of polyurethane comixing hollow-fibre membrane and manufacture method thereof, polyurethane and polyolefin polymers (comprising Kynoar and polyacrylonitrile) blend, and can add inorganic compound (calcium carbonate, silica or simple substance carbon), as blending extrusion equipment, adopt the method for melt spinning-stretching pore-forming to make the polyurethane comixing hollow-fibre membrane with double screw extruder.Do not need any solvent and additive in the film-forming process, manufacture method is simple, and relative cost is lower, environmentally safe.Doughnut film strength with the preparation of the method for melt spinning-stretching pore-forming is higher, but because tear by pulling force in the hole on the wall forms, the out-of-shape in hole, the size in hole and skewness, the size in hole is difficult to control.
Thermally induced phase separation technique is the manufacture method of a kind of hollow-fibre membrane of getting up of developed recently, it is at high temperature polymer and diluent or inorganic pore former etc. to be mixed, form homogeneous phase solution, then be extruded into doughnut, in cooling procedure, solid-liquid phase can occur and separate and liquid-liquid phase separation in system.After phase-splitting, System forming is take polymer as continuous phase, and diluent and inorganic pore former are the two phase structure of decentralized photo, at this moment selects suitable extractant that diluent and inorganic pore former are extracted again.With the hollow-fibre membrane of thermally induced phase separation technique preparation, additive diluent and inorganic pore former all are extracted, and the hollow-fibre membrane after the last moulding only contains polymer, so film strength is high, and the porosity of film is high, flux is high.Thermoplastic polyurethane is made the existing patent report of spinning technique that hollow-fibre membrane adopts phase separation method and melt spinning-stretching hole forming method, has no report but prepare thermoplastic polyurethane hollow fiber membrane with thermally induced phase separation technique.The present invention adopts thermally induced phase separation technique to prepare thermoplastic polyurethane hollow fiber membrane, and the hollow-fibre membrane flexibility that makes is good, and intensity is high simultaneously, and porosity is high, flux is large.
Summary of the invention
One object of the present invention is to provide a kind of thermoplastic polyurethane hollow fiber membrane, and the characteristics of this hollow-fibre membrane maximum are to have higher intensity to have simultaneously good flexibility.
A kind of thermoplastic polyurethane hollow fiber membrane, it comprises the component of following percetage by weight:
Thermoplastic polyurethane: 99.5～99.9%
Antioxidant: 0.1～0.5%.
Preferably, described thermoplastic polyurethane is the extrusion grade resin.
Preferably, described antioxidant is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecanol ester, 1,3,5-trimethyl-2,4, in 6-three (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites one or more.
Another object of the present invention provides a kind of thermally induced phase separation preparation technology of thermoplastic polyurethane hollow fiber membrane, and preparation process is as follows:
(1) thermoplastic polyurethane, diluent, inorganic pore former, antioxidant are mixed, and with the material melting in 175～210 ℃ that stirs, and extrude and make pellet;
(2) then, described pellet 170～230 ℃ of meltings, and is extruded into doughnut, then enters 25～70 ℃ tank cooling forming;
(3) last, add respectively an amount of diluent extractant and inorganic pore former extractant diluent and the inorganic pore former of cooled doughnut the inside are extracted, obtain thermoplastic polyurethane hollow fiber membrane.
Described raw materials comprises the component of following percentage by weight:
Thermoplastic polyurethane: 30～55%
Diluent: 15～45%
Inorganic pore former: 0～30%
Antioxidant: 0.1～0.5%.
Preferably, described diluent is selected from one or more in o-phthalic acid dibutyl ester, diisooctyl phthalate, dibutyl phthalate, repefral, phthalic acid two isodecyl fat, dioctyl adipate, the epoxidized soybean oil.
Preferably, described inorganic pore former is selected from one or more in nano-calcium carbonate, gas phase nano silica, nano zine oxide, the nanomete talc powder.
Preferably, described diluent extractant is selected from one or more in ethanol, n-hexane, cyclohexane, the carrene.
Preferably, described inorganic pore former extractant is selected from one or more in hydrochloric acid, sulfuric acid, NaOH, the potassium hydroxide.
Thermoplastic polyurethane hollow fiber membrane of the present invention adopts the preparation of thermally induced phase separation technique, compare with traditional phase separation method technique and melt spinning-stretching hole forming method technique, the doughnut film-strength of thermally induced phase separation preparation is higher, flux is higher, pore size and being more evenly distributed.The present invention adopts the again technique of extrusion molding hollow-fibre membrane of first granulation, on the one hand, by the double screw extruder granulation mainly be first to material carry out mixing evenly, on the other hand, the product size of extruding by single screw extrusion machine is more stable, and particularly nano level inorganic pore former is not easy to disperse because particle diameter is little, adopt the method for first granulation can make inorganic pore former dispersion more even, the pore size distribution of the hollow-fibre membrane of preparation is more even; And, adopt single screw extrusion machine to make the material of extruding more stable, the inside/outside diameter size of the hollow-fibre membrane of moulding is more even.
Simultaneously, the hot strength of the thermoplastic polyurethane hollow fiber membrane of the present invention's preparation is 7.5～22MPa; The flexibility of hollow-fibre membrane is good, and elongation at break is 200～350%; Flux is high, and pure water flux is 500～2750L/M
2H (0.1MPa, 25 ℃); Pore size and being evenly distributed, pore size is controlled, bubble point pressure 0.20～0.36MPa.It is good that the polyurethane hollow fiber film of the present invention preparation has a chemical-resistance, cleans easily; Need not add the hydrophilic modifying agent, have permanent hydrophilic, can the dry state preservation etc. advantage.The thermoplastic polyurethane hollow fiber membrane of the present invention's preparation can be applied to filtration treatment and the purification of family expenses and commercial Drinking Water Filtration processing, wine brewing, food and medicine, municipal tap water and sewage disposal, trade effluent is processed, the aspects such as pre-treatment of desalinization.
The specific embodiment
The invention provides a kind of thermoplastic polyurethane hollow fiber membrane, it comprises the component of following percetage by weight: thermoplastic polyurethane: 99.5～99.9% and antioxidant: 0.1～0.5%.
Wherein, described thermoplastic polyurethane is the extrusion grade resin.Described antioxidant is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecanol ester, 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
The present invention adopts thermally induced phase separation to prepare described thermoplastic polyurethane hollow fiber membrane, and preparation process comprises the steps:
(1) thermoplastic polyurethane, diluent, inorganic pore former, antioxidant are mixed, and with the material melting in 175～210 ℃ that stirs, and extrude and make pellet;
(2) then, described pellet 170～230 ℃ of meltings, and is extruded into doughnut, then enters 25～70 ℃ tank cooling forming;
(3) last, add respectively an amount of diluent extractant and inorganic pore former extractant diluent and the inorganic pore former of cooled doughnut the inside are extracted, obtain thermoplastic polyurethane hollow fiber membrane.
In step (1), the melting in double screw extruder of the material of described mixing, and extrude and make pellet.
In step (2), described pellet is in the single screw extrusion machine melting, and extrudes and make doughnut.
Wherein, described raw materials comprises the component of following percentage by weight: thermoplastic polyurethane: 30～55%; Diluent: 15～45%; Inorganic pore former: 0～30%; Antioxidant: 0.1～0.5%.
Preferably, the draw ratio of described double screw extruder is 32: 1 (draw ratio: spiro rod length and diameter ratio).The draw ratio of described single screw extrusion machine is 24: 1 (draw ratio: spiro rod length and diameter ratio).
The present invention is by adopting the thermally induced phase separation preparation to include the thermoplastic polyurethane hollow fiber membrane of thermoplastic polyurethane, in preparation process, adopted the technique of extrusion molding after the first granulation, double screw extruder is made pellet and single screw extrusion machine is extruded into doughnut with sequentially passing through behind the described raw material blending, carry out again cooling forming and extraction process, to obtain the thermoplastic polyurethane hollow fiber membrane finished product.
The below further is illustrated the present invention with specific embodiment.
Embodiment 1: take by weighing by weight 43% thermoplastic polyurethane, 24% o-phthalic acid dibutyl ester, 11% dioctyl adipate, 21.7% nano-calcium carbonate, 0.1% 4 [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2% tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, mix with mixer, the material that mixes is through 200 ℃, draw ratio is that 32: 1 double screw extruder melt extrudes granulation, material after the granulation is through 210 ℃, draw ratio is that 24: 1 single screw extrusion machine melt extrudes, through the bushing type spinning head, the spinning head central tube passes into nitrogen, be extruded into doughnut, then the air distance through 15cm enters 40 ℃ of tank cooling formings, and the doughnut after the moulding is collected with wire wrapping wheel.Doughnut after the collection extracts diluent o-phthalic acid dibutyl ester, dioctyl adipate and inorganic pore former calcium carbonate with ethanol and hydrochloric acid respectively, the external diameter 1.25mm of the thermoplastic polyurethane hollow fiber membrane that makes, internal diameter 0.63mm, porosity 73%, bubble point pressure is 0.29MPa, pure water flux is 1350L/m2hr (0.1MPa, 25 ℃), and hot strength 16.8MPa, extension at break are 240%.
Embodiment 2: take by weighing by weight 50% thermoplastic polyurethane, 25% o-phthalic acid dibutyl ester, 10% dibutyl phthalate, 14.7% nano-calcium carbonate, 0.1% 4 [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2% tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, mix with mixer, the material that mixes is through 210 ℃, draw ratio is that 32: 1 double screw extruder melt extrudes granulation, material after the granulation is through 215 ℃, draw ratio is that 24: 1 single screw extrusion machine melt extrudes, through the bushing type spinning head, the spinning head central tube passes into nitrogen, be extruded into doughnut, then the air distance through 15cm enters 30 ℃ of tank cooling formings, and the doughnut after the moulding is collected with wire wrapping wheel.Doughnut after the collection extracts diluent o-phthalic acid dibutyl ester, dibutyl phthalate and inorganic pore former calcium carbonate with ethanol and hydrochloric acid respectively, the thermoplastic polyurethane hollow fiber membrane external diameter 1.24mm that makes, internal diameter 0.64mm, porosity 70%, bubble point pressure is 0.30MPa, pure water flux is 1185L/m2hr (0.1MPa, 25 ℃), and hot strength 14.8MPa, extension at break are 260%.
Embodiment 3: take by weighing by weight 40% thermoplastic polyurethane, 25% diisooctyl phthalate, 15% dibutyl phthalate, 19.7% gas phase nano silica, 0.1% β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecanol ester, 0.2% tricresyl phosphite (2, the 4-di-tert-butyl-phenyl) ester, mix with mixer, the material that mixes is through 175 ℃, draw ratio is that 32: 1 double screw extruder melt extrudes granulation, material after the granulation is through 170 ℃, draw ratio is that 24: 1 single screw extrusion machine melt extrudes, through the bushing type spinning head, the spinning head central tube passes into nitrogen, be extruded into doughnut, then the air distance through 15cm enters 25 ℃ of tank cooling formings, and the doughnut after the moulding is collected with wire wrapping wheel.Doughnut after the collection extracts diluent diisooctyl phthalate, dibutyl phthalate and inorganic pore former silica with n-hexane and NaOH respectively.The thermoplastic polyurethane hollow fiber membrane external diameter 1.26mm that makes, internal diameter 0.64mm, porosity 75%, bubble point pressure is 0.27MPa, pure water flux is 1860L/m
2Hr (0.1MPa, 25 ℃), hot strength 12.7MPa, extension at break are 235%.
Embodiment 4: take by weighing by weight 37% thermoplastic polyurethane, 30% diisooctyl phthalate, 15% epoxidized soybean oil, 17.7% gas phase nano silica, 0.1% 4 [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, 0.2% pair of (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites, mix with mixer, the material that mixes is through 180 ℃, draw ratio is that 32: 1 double screw extruder melt extrudes granulation, material after the granulation is through 185 ℃, draw ratio is that 24: 1 single screw extrusion machine melt extrudes, through the bushing type spinning head, the spinning head central tube passes into nitrogen, be extruded into doughnut, then the air distance through 15cm enters 32 ℃ of tank cooling formings, and the doughnut after the moulding is collected with wire wrapping wheel.Hollow fibre filament after the collection extracts diluent diisooctyl phthalate, epoxidized soybean oil and inorganic pore former silica with n-hexane and NaOH respectively.The thermoplastic polyurethane hollow fiber membrane external diameter 1.23mm that makes, internal diameter 0.63mm, porosity 79%, bubble point pressure is 0.26MPa, pure water flux is 2100L/m
2Hr (0.1MPa, 25 ℃), hot strength 9.7MPa, extension at break are 220%.
Can find out from the various embodiments described above, the thermoplastic polyurethane of corresponding proportion, diluent, inorganic pore former, antioxidant etc. are added mixing in the mixer, and the material behind the mixing sequentially is extruded into doughnut through double screw extruder extruding pelletization and single screw extrusion machine, melt temperature is controlled at respectively in 175～210 ℃ and 170～230 ℃, then it is inserted 25～70 ℃ of tanks and carry out cooling forming, at last, again diluent and the inorganic pore former of the inside of the doughnut after the moulding are extracted, obtain thermoplastic polyurethane hollow fiber membrane.Adopting respectively twin-screw and single screw extrusion machine to be extruded into doughnut through first extruding pelletization makes various raw materials mixing more even again, with the aperture that reaches suitable and be evenly distributed, hot strength and the elongation at break of the hollow-fibre membrane that assurance is obtained are higher, and water flux is also large.
Its each parameter of thermoplastic polyurethane hollow fiber membrane by said method preparation is all in following scope: the hot strength of described hollow-fibre membrane is 7.5～22MPa, elongation at break 200～350%; Pure water flux is 500～2750L/M
2H (0.1MPa, 25 ℃); Bubble point pressure 0.20～0.36MPa.Thermoplastic polyurethane hollow fiber membrane of the present invention is compared with existing filter membrane, and its water flux is higher, and film strength is better.Filter membrane of the present invention has pore size and is evenly distributed, and pore size is controlled, and it is good to have a chemical-resistance, cleans easily; Need not add the hydrophilic modifying agent, have permanent hydrophilic, can the dry state preservation etc. advantage.
The above only is preferred embodiment of the present invention, and is in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (9)
1. thermoplastic polyurethane hollow fiber membrane, it is characterized in that: it comprises the component of following percetage by weight:
Thermoplastic polyurethane: 99.5～99.9%
Antioxidant: 0.1～0.5%
The hot strength of described hollow-fibre membrane is 7.5～22 MPa, elongation at break 200～350%; Under 0.1MPa, 25 ℃ condition, pure water flux is 500～2750L/M
2H; Bubble point pressure 0.20～0.36MPa.
2. described thermoplastic polyurethane hollow fiber membrane according to claim 1 is characterized in that described thermoplastic polyurethane is the extrusion grade resin.
3. described thermoplastic polyurethane hollow fiber membrane according to claim 1, it is characterized in that: described antioxidant is selected from four [β-(3 ', 5 '-di-t-butyl-4 '-hydroxy phenyl) propionic acid] pentaerythritol ester, β-(4 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl) propionic acid octadecanol ester, 1,3,5-trimethyl-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) one or more in benzene, tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester, two (2.4-di-tert-butyl-phenyl) pentaerythritol diphosphites.
4. the preparation method of a thermoplastic polyurethane hollow fiber membrane adopts the thermally induced phase separation preparation, and preparation process is as follows:
(1) thermoplastic polyurethane, diluent, inorganic pore former, antioxidant are mixed, and with the material melting in 175～210 ℃ that stirs, and extrude and make pellet;
(2) then, described pellet 170～230 ℃ of meltings, and is extruded into doughnut, then enters 25～70 ℃ tank cooling forming;
(3) last, add respectively an amount of diluent extractant and inorganic pore former extractant diluent and the inorganic pore former of cooled doughnut the inside are extracted, obtain thermoplastic polyurethane hollow fiber membrane.
5. described preparation method according to claim 4 is characterized in that: in step (1), and the melting in double screw extruder of the material of described mixing, and extrude and make pellet.
6. described preparation method according to claim 4 is characterized in that: in step (2), described pellet is in the single screw extrusion machine melting, and is extruded into doughnut.
7. described preparation method according to claim 4 is characterized in that described raw materials comprises the component of following percentage by weight:
Thermoplastic polyurethane: 30～55%
Diluent: 15～45%
Inorganic pore former: 0～30%
Antioxidant: 0.1～0.5%.
8. described preparation method according to claim 4, it is characterized in that: described diluent extractant is selected from one or more in ethanol, n-hexane, cyclohexane, the carrene; Inorganic pore former extractant is selected from one or more in hydrochloric acid, sulfuric acid, NaOH, the potassium hydroxide.
9. described preparation method according to claim 7, it is characterized in that: described diluent is selected from one or more in o-phthalic acid dibutyl ester, diisooctyl phthalate, dibutyl phthalate, repefral, phthalic acid two isodecyl fat, dioctyl adipate, the epoxidized soybean oil; Described inorganic pore former is selected from one or more in nano-calcium carbonate, gas phase nano silica, nano zine oxide, the nanomete talc powder.
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| CN102343224B (en) * | 2011-08-05 | 2013-07-03 | 武汉纺织大学 | Method for forming porous polyurethane membrane |
| CN103894079B (en) * | 2012-12-29 | 2016-02-24 | 深圳市泉汇来净水科技有限公司 | The preparation method of polyurethane-base hollow fiber ultrafiltration membrane and goods thereof |
| CN105435645B (en) * | 2014-07-22 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of composite nanometer filtering film and preparation method thereof |
| CN105561812A (en) * | 2014-10-09 | 2016-05-11 | 中国石油化工股份有限公司 | Oxidation-resistant polyacrylonitrile ultrafiltration membrane and preparation method thereof |
| WO2016178378A1 (en) * | 2015-05-07 | 2016-11-10 | 住友電気工業株式会社 | Method for operating filtration device, and filtration device |
| CN106554591A (en) * | 2015-09-30 | 2017-04-05 | 中国石油化工股份有限公司 | Modified polyacrylonitrile with lasting oxidative resistance and preparation method thereof |
| CN106867017B (en) * | 2015-12-11 | 2021-02-19 | 东丽纤维研究所（中国）有限公司 | Microporous membrane with controllable pore diameter and preparation method thereof |
| CN106268041B (en) * | 2016-09-09 | 2019-05-28 | 上海科力玛数据科技有限公司 | It is a kind of for purifying the composite material and preparation method and application of air |
| CN108654384A (en) * | 2017-03-31 | 2018-10-16 | 中国石油化工股份有限公司 | Modified polyacrylonitrile and preparation method thereof with lasting oxidative resistance |
| CN113693826B (en) * | 2021-08-30 | 2022-09-09 | 福建恒安卫生材料有限公司 | Sanitary article |
| CN113491962B (en) * | 2021-09-09 | 2022-02-22 | 北京宝盛通国际电气工程技术有限公司 | Forward osmosis membrane and method for producing same |
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| CN101406812A (en) * | 2008-11-04 | 2009-04-15 | 东华大学 | Method for producing thermoplastic polyurethane elastomer/polyvinylidene fluoride blended hollow fiber film |
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| CN101406812A (en) * | 2008-11-04 | 2009-04-15 | 东华大学 | Method for producing thermoplastic polyurethane elastomer/polyvinylidene fluoride blended hollow fiber film |
| CN101439269A (en) * | 2008-12-04 | 2009-05-27 | 南昌航空大学 | Method for preparing thermoplastic polyurethane elastic hollow fiber membrane |
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