CN102151500A - PVDF/TPEE/PES ternary blended hollow fiber ultra-filtration membrane and preparation method - Google Patents
PVDF/TPEE/PES ternary blended hollow fiber ultra-filtration membrane and preparation method Download PDFInfo
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- CN102151500A CN102151500A CN201110053803XA CN201110053803A CN102151500A CN 102151500 A CN102151500 A CN 102151500A CN 201110053803X A CN201110053803X A CN 201110053803XA CN 201110053803 A CN201110053803 A CN 201110053803A CN 102151500 A CN102151500 A CN 102151500A
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- 239000012528 membrane Substances 0.000 title claims abstract description 37
- 229920006346 thermoplastic polyester elastomer Polymers 0.000 title claims abstract description 34
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 33
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 239000002033 PVDF binder Substances 0.000 title claims abstract 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract 9
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 11
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000003607 modifier Substances 0.000 claims abstract description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 14
- 229920002959 polymer blend Polymers 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 9
- 230000001112 coagulating effect Effects 0.000 claims description 8
- 238000009987 spinning Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920003208 poly(ethylene sulfide) Polymers 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical group CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000036571 hydration Effects 0.000 claims description 3
- 238000006703 hydration reaction Methods 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000010618 wire wrap Methods 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 abstract description 27
- 229920000642 polymer Polymers 0.000 abstract description 10
- 230000004907 flux Effects 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 abstract description 3
- 229920000728 polyester Polymers 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- 108091003079 Bovine Serum Albumin Proteins 0.000 description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 3
- 229940098773 bovine serum albumin Drugs 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000003373 anti-fouling effect Effects 0.000 description 2
- 235000012489 doughnuts Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyvinylidene fluoride (PVDF)/ thermoplastic polyester elastomer (TPEE)/ polyether sulfone (PES) ternary blended hollow fiber ultra-filtration membrane and a preparation method thereof. The aperture of the PVDF/TPEE/PES ternary blended hollow fiber ultra-filtration membrane is 0.01 to 0.1 micron. The hollow fiber ultra-filtration membrane comprises PVDF, TPEE, PES, hydrophilic modifier and pore forming agent serving as main components. The PVDF/TPEE/PES ternary blended hollow fiber ultra-filtration membrane prepared by using the method integrates the characteristics of three high polymers, and has the advantages of high strength, good toughness, good heat resistance, excellent pollution resistance and high flux.
Description
Technical field
The present invention discloses a kind of PVDF/TPEE/PES tertiary blending hollow fiber ultrafiltration membrane and preparation method, the invention belongs to the membrane separation technique field.
Background technology
Kynoar (PVDF) is a kind of crystalline polymer, has good mechanical strength, outstanding uvioresistant and weather proof characteristic, and it also has excellent chemical stability in addition, is present better membrane material.But in use there is following problem in the PVDF hollow fiber ultrafiltration membrane of one-component: (1) PVDF milipore filter hydrophily is poor, easily pollutes; (2) water flux of film and rejection can not improve simultaneously; (3) mechanical strength of film is not high, thereby in use fracture of wire takes place easily.
Polyester (TPEE) (thermoplastic polyester elastomer) is the block copolymer that contains hard section of polyester and polyester soft segment.Wherein polyester soft segment and uncrystallized polyester form the hard section of amorphous phase polyester partially crystallizable and form the crystallization microcell, play physical crosslinking point.TPEE has the elasticity of rubber and the intensity of engineering plastics; Give its elasticity for soft section, make it resemble rubber; Hard section is given its processing characteristics, makes it resemble plastics; With the rubber phase ratio, it has better processability energy and longer service life; Compare with the engineering material, have advantages of high strength equally, and pliability and dynamic mechanical are better.Simultaneously, have good hydrophilicity, with PVDF can be compatible well, it is poor to remedy its hydrophily, easily shortcoming such as pollution.
Polyether sulfone PES is a kind of high polymer that contains aromatic rings, have favorable rigidity, mechanical strength, acid-proof alkaline, the close property of resistance to compression, chemical stability, hear resistance (can in 0-100 ℃ of scopes, use), the applied widely and higher advantages such as anti-oxidant and chlorine resistance energy of PH, but still there is defective when using in the tunica fibrosa that single component makes; Chinese patent literature CN1375351 discloses a kind of manufacture method of blend polyethersulfone doughnut dialysis membrane, and it uses polyether sulfone is main material of preparing, and uses other high polymer to carry out blend to make.
By above-mentioned analysis as can be known, the tunica fibrosa that above-mentioned each polymer makes respectively a lot of problems are arranged in the use, and the inventor is with above-mentioned multiple polymers blending and modifying, makes the PVDF/TPEE/PES blend hollow fiber membrane, so proposition of the present invention is just arranged.
Summary of the invention
At the deficiencies in the prior art, a kind of a kind of PVDF/TPEE/PES blend hollow fiber ultrafiltration membrane with high strength, high water flux and high anti-soil that provides is provided, because it has kept the good characteristic of every kind of polymer, can solve the contradiction of rigidity, toughness, contamination resistance, water flux, rejection mutual restriction under optimum conditions.
For achieving the above object, the present invention is achieved by the following technical solutions:
A kind of tertiary blending hollow fiber ultrafiltration membrane comprises following component by weight percentage:
A, polymer blend 16-25%;
B, hydrophilic modifying agent 5-10%;
C, pore former 6-10%;
D, solvent 65-75%;
Wherein, described polymer blend is that PVDF, TPEE, PES form.
Further: described polymer blend is made up of PVDF, TPEE and PES, and by weight percentage, blending ratio is 10-20%:5-15%:1-8%.
Further, described hydrophilic modifier be in polyethylene glycol PEG, polyvinylpyrrolidine cave PVP, the propane diols one or more.
Further, described pore former is one or more in lithium chloride, a hydration lithium chloride, acetone, the water.
Further, described solvent is dimethyl formamide DMF, dimethylacetylamide DMAC, N, N-dimethyl pyrrolidone NMP, one or more among the dimethyl sulfoxide (DMSO) DMSO.
A kind of preparation method of PVDF/TPEE/PES blend hollow fiber ultrafiltration membrane, step is as follows: said mixture is added thermal agitation at 60-90 ℃, dissolving evenly makes casting solution, under the certain vacuum state, 30-60 ℃ of deaeration 3-6h is by the spinning of doughnut spinning-drawing machine, enter then in the outer coagulating bath, solvent and pore former enter and solidify liquid phase, and polymer and hydrophilizing agent solidify as the rich phase of polymer, form hollow fiber ultrafiltration membrane.
The invention has the beneficial effects as follows: the present invention fills a prescription simply, have stronger toughness, rigidity, chemical resistance, hear resistance, antifouling property, water flux with the prepared PVDF/TPEE/PES tertiary blending of the inventive method hollow fiber ultrafiltration membrane and obviously improve, and the unlikely decline of rejection.The prepared PVDF/TPEE/PES hollow fiber ultrafiltration membrane of the inventive method anti-pressure ability is strong, be applicable to external pressure operation type hyperfiltration membrane assembly, the rivers surface water deep purifying that can use printing and dyeing, plating, contains object height is admittedly handled, and can be widely used in numerous industries such as medicine, chemical industry, beverage, food, sewage disposal in addition.
The specific embodiment
By will helping to understand the present invention, but do not limit content of the present invention to following examples.
Embodiment: a kind of tertiary blending hollow fiber ultrafiltration membrane comprises following component by weight percentage:
A, polymer blend 16-25%;
B, hydrophilic modifying agent 5-10%;
C, pore former 6-10%;
D, solvent 65-75%;
Wherein, described polymer blend is made up of PVDF, TPEE and PES, and by weight percentage, blending ratio is 10-20%:5-15%:1-8%. Hydrophilic modifier be in polyethylene glycol PEG, polyvinylpyrrolidine cave PVP, the propane diols one or more; Pore former is one or more in lithium chloride, a hydration lithium chloride, acetone, the water; Solvent is dimethyl formamide DMF, dimethylacetylamide DMAC, N, N-dimethyl pyrrolidone NMP, one or more among the dimethyl sulfoxide (DMSO) DMSO.
A kind of preparation method of PVDF/TPEE/PES blend hollow fiber ultrafiltration membrane, step is as follows:
In weight ratio, take by weighing the polymer blend of 16-25% earlier, pour in the reactor, add the hydrophilic modifying agent of 5-10%, the pore former of 6-10% and the solvent of 65-75% more successively, stir 3-8h at 60-90 ℃ of constant temperature, fully dissolving; Constant temperature leaves standstill 1-4h in 30-60 ℃ of water-bath, and vacuum defoamation can obtain the standard casting solution; Casting solution is extruded through special spinning nozzle under the pressure of 0.20-0.35Mpa, enters coagulating bath behind the vertical mobile 5-10cm in air; Coagulating bath is made up of pure water, and temperature is at 10-40 ℃; Regulate the wire wrapping wheel rotating speed, spinning speed is controlled at 12m/min, can obtain PVDF/TPEE/PES blend hollow fiber ultrafiltration membrane.
The present invention discloses a kind of PVDF/TPEE/PES blend hollow fiber ultrafiltration membrane and preparation method thereof, and described PVDF/TPEE/PES blend hollow fiber ultrafiltration membrane aperture is at 0.01-0.1 μ m.The Main Ingredients and Appearance of described PVDF/TPEE/PES blend hollow fiber membrane is Kynoar (PVDF), polyester (TPEE), polyether sulfone PES, hydrophilic modifying agent, pore former.The prepared PVDF/TPEE/PES blend of the inventive method hollow fiber ultrafiltration membrane, the characteristics of comprehensive three kinds of high polymers, not only intensity is big, good toughness, and good heat resistance, antifouling property are good, and flux is big.
By following embodiment (embodiment 1, comparative example 1 and comparative example 2) contrast, more the advantage that the PVDF/TPEE/PES blend hollow fiber membrane has can be described, specific as follows:
Embodiment 1
Prepare burden by following component and composition: PVDF 10%; TPEE 10%; PES 2%; PEG-400 6.0%; LiCl 3%; DMAc 69%.Above-mentioned raw materials is added in the dissolvers, add thermal agitation at 70 ℃, dissolving evenly makes casting solution, and deaeration 4h under the vacuum condition makes the standard casting solution; Casting solution is extruded through spinning nozzle under the pressure of 0.35Mpa, after air stops 2-3s, enter 25 ℃ pure water coagulating bath again, soak back taking-up more than 2 days, residue and bacterium on the clear water flush away film silk, protect the hole with 30% glycerine then and handle, soaked 24 hours, dry get final product PVDF/TPEE/PES tertiary blending hollow fiber ultrafiltration membrane.At ambient temperature, utilizing the stretching strength determination instrument that film is carried out fracture strength measures.Recording film strength is 15Mpa, 5 times of draw ratios.Pure water flux is 400LMH, bovine serum albumin rejection 90%;
The comparative example 1
Prepare burden by following component and composition: PVDF 10%; TPEE 10%; PEG-400 6.0%; LiCl 3%; DMAc 71%.Above-mentioned raw materials is added in the dissolvers, add thermal agitation at 70 ℃, dissolving evenly makes casting solution, and deaeration 4h under the vacuum condition makes the standard casting solution; Casting solution is extruded through spinning nozzle under the pressure of 0.35Mpa, after air stops 2-3s, enter 25 ℃ pure water coagulating bath again, soak back taking-up more than 2 days, residue and bacterium on the clear water flush away film silk, protect the hole with 30% glycerine then and handle, soaked 24 hours, dry get final product PVDF/TPEE/PES tertiary blending hollow fiber ultrafiltration membrane.At ambient temperature, utilizing the stretching strength determination instrument that film is carried out fracture strength measures.Recording film strength is 10Mpa, 6 times of draw ratios.Pure water flux is 450LMH, bovine serum albumin rejection 90%;
The comparative example 2
Prepare burden by following component and composition: PVDF 18%; PES 2%; PEG-400 6.0%; LiCl 3%; DMAc 71%.Above-mentioned raw materials is added in the dissolvers, add thermal agitation at 70 ℃, dissolving evenly makes casting solution, and deaeration 4h under the vacuum condition makes the standard casting solution; Casting solution is extruded through spinning nozzle under the pressure of 0.35Mpa, after air stops 2-3s, enter 25 ℃ pure water coagulating bath again, soak back taking-up more than 2 days, residue and bacterium on the clear water flush away film silk, protect the hole with 30% glycerine then and handle, soaked 24 hours, dry get final product PVDF/PES binary blend hollow fiber ultrafiltration membrane.At ambient temperature, utilizing the stretching strength determination instrument that film is carried out fracture strength measures.Recording film strength is 10Mpa, 1 times of draw ratio.Pure water flux is 300LMH, bovine serum albumin rejection 90%.
The above record only for utilizing the embodiment of this origination techniques content, anyly is familiar with change, the variation that this technology person uses this creation to make, and all belongs to the claim of this creation opinion, and is not limited to those disclosed embodiments.
Claims (6)
1. tertiary blending hollow fiber ultrafiltration membrane is characterized in that comprising by weight percentage following component:
A, polymer blend 16-25%;
B, hydrophilic modifying agent 5-10%;
C, pore former 6-10%;
D, solvent 65-75%;
Wherein, described polymer blend is that PVDF, TPEE, PES form.
2. tertiary blending hollow fiber ultrafiltration membrane according to claim 1 is characterized in that: described polymer blend is made up of PVDF, TPEE and PES, and by weight percentage, blending ratio is 10-20%:5-15%:2-5%.
3. tertiary blending hollow fiber ultrafiltration membrane according to claim 1 is characterized in that: described hydrophilic modifier be in polyethylene glycol PEG, polyvinylpyrrolidine cave PVP, the propane diols one or more.
4. tertiary blending hollow fiber ultrafiltration membrane according to claim 1 is characterized in that: described pore former is one or more in lithium chloride, a hydration lithium chloride, acetone, the water.
5. tertiary blending hollow fiber ultrafiltration membrane according to claim 1 is characterized in that: described solvent is dimethyl formamide DMF, dimethylacetylamide DMAC, N, N-dimethyl pyrrolidone NMP, one or more among the dimethyl sulfoxide (DMSO) DMSO.
6. the preparation method of claim 1 to 5 tertiary blending hollow fiber ultrafiltration membrane, its step is as follows: in weight ratio, take by weighing the polymer blend of 16-25% earlier, pour in the reactor, add the hydrophilic modifying agent of 5-10%, the pore former of 6-10% and the solvent of 65-75% more successively, stir 3-8h at 60-90 ℃ of constant temperature, fully dissolving; Constant temperature leaves standstill 1-4h in 30-60 ℃ of water-bath, and vacuum defoamation can obtain the standard casting solution; Casting solution is extruded through spinning nozzle under the pressure of 0.20-0.35Mpa, enters coagulating bath behind the stop 2-3s in air; Coagulating bath is made up of pure water, and temperature is at 10-40 ℃; Regulate the wire wrapping wheel rotating speed, spinning speed is controlled at 12m/min, can obtain PVDF/TPEE/PES blend hollow fiber ultrafiltration membrane.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201110053803XA CN102151500A (en) | 2011-03-07 | 2011-03-07 | PVDF/TPEE/PES ternary blended hollow fiber ultra-filtration membrane and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831019A (en) * | 2014-03-25 | 2014-06-04 | 厦门绿邦膜技术有限公司 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN103831017A (en) * | 2014-02-28 | 2014-06-04 | 成都新柯力化工科技有限公司 | Preparation method of high molecular ultra-filtration membrane |
| CN106000133A (en) * | 2016-06-25 | 2016-10-12 | 贵州省材料技术创新基地 | PSF (polysulfone)-TPE (thermoplastic elastomer)-OMMT (organic montmorillonite) blended hollow fiber membrane and preparation method thereof |
Citations (3)
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|---|---|---|---|---|
| CN1631501A (en) * | 2004-11-11 | 2005-06-29 | 东华大学 | Blended polyethersulfone hollow fiber dialysis ultrafiltration membrane, manufacturing method and use thereof |
| CN1883779A (en) * | 2006-05-19 | 2006-12-27 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN101559326A (en) * | 2009-05-08 | 2009-10-21 | 东华大学 | Nanofibre hyperfiltration membrane and preparation method thereof |
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2011
- 2011-03-07 CN CN201110053803XA patent/CN102151500A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1631501A (en) * | 2004-11-11 | 2005-06-29 | 东华大学 | Blended polyethersulfone hollow fiber dialysis ultrafiltration membrane, manufacturing method and use thereof |
| CN1883779A (en) * | 2006-05-19 | 2006-12-27 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN101559326A (en) * | 2009-05-08 | 2009-10-21 | 东华大学 | Nanofibre hyperfiltration membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| 齐文玉: "PES PVDF共混中空纤维膜的研制", 《纺织科学研究》, no. 1, 31 December 2001 (2001-12-31), pages 41 - 48 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103831017A (en) * | 2014-02-28 | 2014-06-04 | 成都新柯力化工科技有限公司 | Preparation method of high molecular ultra-filtration membrane |
| CN103831017B (en) * | 2014-02-28 | 2015-11-18 | 成都新柯力化工科技有限公司 | A kind of preparation method of polymer ultrafiltration membrane |
| CN103831019A (en) * | 2014-03-25 | 2014-06-04 | 厦门绿邦膜技术有限公司 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN106000133A (en) * | 2016-06-25 | 2016-10-12 | 贵州省材料技术创新基地 | PSF (polysulfone)-TPE (thermoplastic elastomer)-OMMT (organic montmorillonite) blended hollow fiber membrane and preparation method thereof |
| CN106000133B (en) * | 2016-06-25 | 2018-08-28 | 贵州省材料技术创新基地 | Polysulfones-thermoplastic elastomer (TPE)-organo montmorillonite blend hollow fiber membrane and preparation method thereof |
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Application publication date: 20110817 |