CN102397760B - Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof - Google Patents
Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof Download PDFInfo
- Publication number
- CN102397760B CN102397760B CN201010278600.6A CN201010278600A CN102397760B CN 102397760 B CN102397760 B CN 102397760B CN 201010278600 A CN201010278600 A CN 201010278600A CN 102397760 B CN102397760 B CN 102397760B
- Authority
- CN
- China
- Prior art keywords
- preparation
- water
- polyether sulfone
- pure water
- pore former
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a polyether sulfone hollow fiber ultrafiltration membrane and a preparation method thereof. The preparation method of the polyether sulfone hollow fiber ultrafiltration membrane comprises steps that: polyether sulfone resin, a polar solvent, a non-polar micro-molecular pore-forming agent and an inorganic salt or oxide pore-forming agent are prepared into a membrane casting solution; a hollow fiber membrane is prepared through a non-solvent phase separation method (NIPS) dry-wet spinning technology; the hollow fiber membrane is washed by using pure water, and extracted by using inorganic acid, such that the organic micro-molecular pore-forming agent, the inorganic salt pore-forming agent, the oxide pore-forming agent and the solvent are completely removed. The prepared polyether sulfone hollow fiber membrane filaments comprise no other extraneous material except the polyether sulfone material, such that the purity of a system after filtration is ensured. The prepared ultrafiltration membrane can be stored after being dried by baking, such that multiplication of bacteria and microbe under a wet state can be avoided. Therefore, the ultrafiltration membrane is advantaged in safer application, wider purposes, and more convenient application. The preparation method is suitable for large-scale industrialized productions.
Description
Technical field
The present invention relates to a kind of PES and preparation method thereof.
Background technology
Polyethersulfone resin (PES) is a kind of special engineering plastics, because its vitrification point is high, and materialization good stability, the milipore filter that can prepare is withstand voltage, heat-resisting, and oxidative resistance is all higher, and Bc is also good compared with other membrane material.In recent years, membrane separation technique development was swift and violent, and the hollow-fibre membrane of being made by polyether sulfone (PES) has been widely used in industry, and domestic use of water is processed and water purifies, and the filtration of biological medical product.Drinking water particularly, beverage, the purification of drinks and various biological medical product and purifying, the application of the aspect such as separated.(1) Chinese patent CN120183A describes early stage polyether sulphone hollow fibre film and manufacture method and purposes; (2) Chinese patent CN1680010A describes a kind of modified poly (ether-sulfone) (PES) hollow-fibre membrane and manufacture method thereof; (3) preparation method that CN1695777A describes a kind of enhancement mode polyether sulphone hollow fibre film comprises large hydrophilic molecular and organic perforating agent etc.; Above-mentioned all these be to adopt non-solvent phase separation method (NIPS) technique, by often containing a large amount of large molecule organic hydrophilic agent and pore formers in wet method and the made film silk that obtains polyether sulfone (PES) of dry-wet method, because these macromolecular substances are not easy to remove completely from film silk, also much be present in film, so tend to discharge from film silk at leisure in application, although these macromolecular compounds are nontoxic, but in the system after filtration, attracted external component, as caused COD to raise in the water after filtration.Moreover, with polyether sulfone fiber film prepared by non-solvent phase separation method (NIPS) technique, need to preserve in order to avoid the reduction of water flux under hygrometric state, add and in filter membrane, remain more organic macromolecule additive, such fibrous filter membrane is easy to breed bacteria under hygrometric state, mould etc., so this, contain the macromolecular polyether sulfone of organic hydrophilicity (PES) hollow fiber film thread at drinking water, the purification of food and biologics, purify and bring a lot of problems with separated grade in filter process and in the storage process of film, as needs add extra antiseptic and membrane module are needed to frequent sterilization etc.
Summary of the invention
In order to overcome above-mentioned defect, the invention provides a kind of polyether sulfone fiber milipore filter that does not contain any additive, need to not preserve under hygrometric state.
PES of the present invention, is to be prepared from through the spinning of non-solvent phase separation method with polyether sulfone casting solution, and described polyether sulfone preparation liquid comprises the component of following percetage by weight:
Polyethersulfone resin 15-30%, polar solvent 40-80%, nonpolar little molecule pore former 1-40%,
Inorganic solubility salt or hydrophobic oxide-based pore former 1-20%;
Polyethersulfone resin of the present invention is polyether sulfone or polyethersulfone copolymer, or is the mixture of polyether sulfone and polysulfones.The molecular weight of described polyethersulfone resin is 30,000-60,000 dalton's (weight average molecular weight).
Preferably, described polar solvent is dimethylacetylamide, dimethyl formamide, 1-METHYLPYRROLIDONE or methyl-sulfoxide.
Preferably, described nonpolar little molecule pore former is water, ethanol, ethylene glycol, diethylene glycol, isopropyl alcohol, glycerine or butanols.
Preferably, described inorganic solubility salt is lithium chloride, lithium nitrate, lithium perchlorate or nano-sized hydrophobic calcium carbonate, hydrophobic oxide-based be nano-sized hydrophobic zinc oxide or nano-sized hydrophobic zirconia.
The non-solvent phase separation method preparation method of above-mentioned PES, comprises the steps:
(1) according to the formula of claim 1, take: polyethersulfone resin 15-30%, polar solvent 40-80%, nonpolar little molecule pore former 1-40%, inorganic solubility salt or hydrophobic oxide-based pore former 1-20%, above-mentioned each component is invested in spinning still, stirring and dissolving 8-10 hour at 75-95 ℃, makes the spinning casting solution mixing, and vacuum discontinuous degassing is also held in needed spinning temperature 25-80 ℃;
(2) use the non-solvent phase separation method technique spinning of dry-wet method: casting solution prepared by step (1) filters by the spinning of spray silk mould, spray the spun silk of silk mould coagulation forming in coagulating bath, make polyether sulphone hollow fibre film milipore filter crude product;
(3) the polyether sulphone hollow fibre film milipore filter crude product of step 2 preparation soaks except the inorganic salts pore former in striping silk in rare inorganic acid, then with cleaning and remove residual organic solvent, pore former in 50-60 ℃ of water, finally, after soaking in ethanol and hexane solution successively, 60 ℃ of oven dry.
Preferably, described polar solvent is dimethylacetylamide, dimethyl formamide, 1-METHYLPYRROLIDONE or methyl-sulfoxide.
Preferably, described nonpolar little molecule pore former is water, ethanol, ethylene glycol, diethylene glycol, isopropyl alcohol, glycerine or butanols.
Preferably, described inorganic solubility salt is lithium chloride, lithium nitrate, lithium perchlorate or nano-sized hydrophobic calcium carbonate, hydrophobic oxide-based be nano-sized hydrophobic zinc oxide or nano-sized hydrophobic zirconia.
Preferably, described inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
Preferably, described coagulating bath comprises outer solidification liquid and interior solidification liquid; Described outer solidification liquid is pure water, or the mixed liquor of pure water and ethanol, isopropyl alcohol or ethylene glycol, and the weight percent content of water is not less than 70%; Described interior solidification liquid is pure water, or the mixed liquor of pure water and polar solvent dimethylacetylamide, dimethyl formamide, methyl-sulfoxide or 1-METHYLPYRROLIDONE, and in described mixed liquor, the weight percent content of water is 40-80%.
Preferably, described polyether sulfone preparation liquid comprises the component of following percetage by weight: polyethersulfone resin 15-20%, polar solvent 45-60%, nonpolar little molecule pore former 15-30%, inorganic solubility salt or hydrophobic oxide-based pore former 1-8%.
Preferably, described polyether sulfone preparation liquid comprises the component of following percetage by weight: polyethersulfone resin 20-30%, polar solvent 50-65%, nonpolar little molecule pore former 10-15%, inorganic solubility salt or hydrophobic oxide-based pore former 5-15%.
PES of the present invention, in its formula, each component kind and content draw through concentrating on studies and testing, it is optimized recipe ingredient, polyethersulfone resin is 15-30wt% at the content of spinning casting solution, viscosity lower than 15% spinning casting solution is too low, spinnability is poor, and spun film silk mechanical strength is also poor.Surpass the dissolubility variation of 30% polyethersulfone resin in the polar solvent adopting, and easily produce and be separated.The poor solvent that the nonpolar little molecule pore former adopting is polyethersulfone resin, when adding nonpolar little molecule pore former to surpass 40%, unstable and the easy generation that becomes of spinning casting film is separated, and the inorganic solubility salt of employing and hydrophobic oxide-based pore former can be being better communicated with between fenestra and fenestra and through one in film silk.These inorganic salts are lower from solubility in these solvents, and these inorganic salts cannot form homogeneous solution during supersaturation in solvent, during same hydrophobic nano-oxide supersaturation, can not be dispersed in solution well.Do not dissolve that inorganic salts exists or agglomerating oxide is present in spinning casting solution having, will cause micropore that the surface of the hollow-fibre membrane that forms occurs that defect picture is larger etc.Poly (ether-sulfone) ultrafiltration membrane of the present invention can be dried rear preservation, while using the polyether sulfone fiber filter membrane after drying, first dry film silk is soaked after about 10 minutes in alcohol, film silk is activated, use again a large amount of water soakings after 10 minutes, rinse again to remove residual alcohol, film silk external diameter 0.3-1.5mm after resulting being activated, internal diameter 0.1-1.0mm, wall thickness 0.1-0.5mm, film surface apertures 0.003-0.5 μ m, molecular cut off is that 1000-20000 dalton material reaches 0.5-100%, pure water flux (inner pressed) is 50-1000L/M
2h (at 0.1mPa, 25 degrees Celsius under), the stretch breaking strength of film silk is 3.0-6.0mPa, the compressive resistance > 0.8mPa of Mo Si soaks three months in water, measures the content < 1ppm of COD.
The milipore filter that adopts formula of casting of the present invention to make according to above-mentioned minute solvent phase partition method (NIPS) preparation method, the hollow fiber filter membrane film silk of finally making is pure polyether sulfone, without any extra additive remain in film silk, can definitely guarantee to filter the purity of rear system, milipore filter of the present invention like this can be applied in the filtration approach of multiple fields, as the filtration of drinking water, biological medical product, purification and purification etc.Preparation method's process operation of the present invention and equipment needed thereby are all easier, are suitable for large-scale industrialization and produce.The milipore filter of preparation can be preserved under drying regime, has departed from traditional hygrometric state store method, has obtained the progress of absolute sense, and the milipore filter of preserving after drying can effectively reduce the infection of bacterium and microorganism under hygrometric state, uses saferly, preserves more convenient.
Accompanying drawing explanation
Fig. 1 is the cross section electron-microscope scanning figure of PES of the present invention in embodiment mono-;
Fig. 2 is the cross section electron-microscope scanning figure of the PES of embodiment five preparations;
Fig. 3 is the cross section electron-microscope scanning figure of the hollow fiber film thread of the polyether sulfone that contains hydrophilic macromolecule pore former of preparation in comparative example one.
The specific embodiment
Embodiment and accompanying drawing are introduced to PES of the present invention and preparation method thereof in detail below:
Experimental example one
Polyethersulfone resin (PES) (BASF E6020P molecular weight 55,000 dalton) 18%, dimethylacetylamide 54% (DMAc), diethylene glycol (DEG) 24.5% and hydrophobization nano zine oxide (particle diameter < 30nm) 3.5%.First after diethylene glycol (DEG) slowly being added in dimethylacetylamide (DMAc) solvent, add again pulverous hydrophobic nano nano zine oxide, under high-speed stirred, make inorganic nanometer oxide be suspended in equably in solution, finally add again polyether sulfone (PES) resin, in stirring, be warming up to gradually 80 ℃.And under nitrogen protection, be uniformly mixed after one day, be then cooled to gradually 40 ℃, maintain this temperature stationary vacuum deaeration one day, the macromolecule spinning casting solution that obtains mixing.The solidification liquid of interior adventitia silk moulding is pure water.When spinning casting solution passes through spinning-nozzle mould at certain pressure, the thing of the hollow fiber forming, after air section 10CM, directly enter in 30 ℃ of solidified water baths, the draft speed of spinning is approximately 15m/min, and be there is no the impact of external force, so basic consistent from the extruded velocity of die nozzle with spinning solution.Film silk, after drip washing, soaks after 2 hours in the sulfuric acid of 1.0M, then continues to clean in 50 ℃ of pure water, remove residual solvent, little molecule organic pore former and inorganic ions, be finally taken up in order of priority film silk to be immersed in after alcohol and n-hexane, at 60 ℃ of temperature, dries.The polyether sulphone hollow fibre film external diameter 0.75mm of resulting oven dry, internal diameter 0.58mm, through absolute alcohol, soaking after 10 minutes, with pure water, clean up again, obtain film silk pure water flux (interior pressure): 350L/m2h@0.1mPa, 25 ℃, the fracture tensile strength 4.3mPa of film silk, the compressive resistance of film silk (interior pressure) > 0.8mPa.Polyvinylpyrrolidone (PVP K10, molecular weight 10,000 dalton) rejection is 95%.In pure water, film silk soaks the COD content < 1ppm in water after 3 months.If Fig. 1 is the cross section electron-microscope scanning figure of the PES prepared of the present embodiment.
Embodiment bis-
Adopt formula and the preparation method of embodiment mono-, difference is that inorganic oxide is hydrophobization nano-calcium carbonate (particle diameter < 30nm).Outside the film silk post processing spun is identical with embodiment mono-, with 1M HCl solution, extract calcium carbonate.
The polyether sulphone hollow fibre film external diameter 0.73mm of resulting oven dry, internal diameter 0.57mm, through absolute alcohol, soaking after 10 minutes, with pure water, clean up again, obtain film silk pure water flux (interior pressure): 460L/m2h@0.1mPa, 25 ℃, the fracture tensile strength 4.8mPa of film silk, the compressive resistance of film silk (interior pressure) > 0.8mPa.Polyvinylpyrrolidone (PVP K10, molecular weight 10,000 dalton) rejection is 92%.In pure water, film silk soaks the COD content < 1ppm in water after 3 months.
Embodiment tri-
Adopt formula and the preparation method of embodiment mono-, difference is polyethersulfone resin (BASF E3010 molecular weight is 30,000 dalton).
The polyether sulphone hollow fibre film external diameter 0.73mm of resulting oven dry, internal diameter 0.55mm, after alcohol-pickled 10 minutes, with pure water, clean up again, the film silk pure water flux (interior pressure) obtaining: 535L/m2h@0.1mPa, 25 ℃, the fracture tensile strength 3.6mPa of film silk, the compressive resistance of film silk (interior pressure) > 0.7mPa.Polyvinylpyrrolidone (PVP K10, molecular weight 10,000 dalton) rejection is 86%.In pure water, film silk soaks the COD content < 1ppm in water after 3 months.
Embodiment tetra-
Adopt formula and the preparation method of embodiment mono-, difference is that polyethersulfone resin is (BASF E6020P molecular weight 55,000 dalton) 18%, dimethylacetylamide (DMAC) 53%, diethylene glycol (DEG) 24.5% and lithium chloride (LiCl) 4.5%.First in dimethylacetamide solvent, add after diethylene glycol (DEG), add lithium chloride (LiCl), inorganic salts down to dissolving completely, finally add polyethersulfone resin in high-speed stirred more again, step through identical with embodiment mono-, obtains polyether sulphone hollow fibre film silk.Because inorganic lithium chloride major part enters and solidifies in water-bath in spinning process, so directly, with cleaning in the pure water of 50 ℃, remove residual solvent, the little molecule pore former of organic one-tenth and inorganic ions etc., finally film silk is taken up in order of priority and is immersed in after alcohol and n-hexane, at 60 ℃ of temperature, dry.
The polyether sulphone hollow fibre film external diameter 0.76mm of resulting oven dry, internal diameter 0.52mm, after alcohol-pickled 10 minutes, with pure water, clean up again, obtain film silk pure water flux (interior pressure): 450L/m2h@0.1mPa, 25 ℃, the fracture tensile strength 3.8mPa of film silk, the compressive resistance of film silk (interior pressure) > 0.8mPa.Polyvinylpyrrolidone (PVP K10, molecular weight 10,000 dalton) rejection is 95%.In pure water, film silk soaks the COD content < 1ppm in water after 3 months.
Embodiment five
Adopt formula and the preparation method of embodiment mono-, difference is that the solvent of polyether sulfone spinning casting solution is N-methylpyrrolidone (NMP), nonpolar little molecule pore former is butanols 24.5%, and interior solidification liquid is water and N-methylpyrrolidone (NMP) 50: 50,50 ℃ of spinning temperatures.
The polyether sulphone hollow fibre film external diameter 0.70mm of resulting oven dry, internal diameter 0.5mm, after alcohol-pickled 10 minutes, with pure water, clean up again, obtain film silk pure water flux (interior pressure): 683L/m2h@0.1mPa, 25 ℃, the fracture tensile strength 4.5mPa of film silk, the compressive resistance of film silk (interior pressure) > 0.8mPa.Polyvinylpyrrolidone (PVP K10, molecular weight 10,000 dalton) rejection is 78%.In pure water, film silk soaks the COD content < 1ppm in water after 3 months.If Fig. 2 is the cross section electron-microscope scanning figure of the PES prepared of the present embodiment.
Embodiment six
Adopt formula and the preparation method of embodiment mono-, difference is that nonpolar little molecule pore former is ethanol, and interior solidification liquid is water and dimethylacetylamide (DMAC) 40: 60, and spinning temperature maintains 50 ℃.
The polyether sulphone hollow fibre film external diameter 0.73mm of resulting oven dry, internal diameter 0.52mm, through absolute alcohol, soaking after 10 minutes, with pure water, clean up again, obtain film silk pure water flux (interior pressure): 754L/m2h@0.1mPa, 25 ℃, the fracture tensile strength 4.3mPa of film silk, the compressive resistance of film silk (interior pressure) > 0.8mPa.Polyvinylpyrrolidone (PVP K10, molecular weight 10,000 dalton) rejection is 75%.In pure water, film silk soaks the COD content < 1ppm in water after 3 months.
Embodiment seven
Adopt formula and the preparation method of embodiment mono-, difference is that the formula of macromolecule spinning casting solution is polyethersulfone resin (BASFE6020, molecular weight 55,000 dalton) 17%, dimethylacetylamide (DMAC) 78%, water 5%.Inside and outside solidification liquid component is identical with embodiment mono-with spinning temperature, and spinning temperature maintains 30 ℃.
The polyether sulphone hollow fibre film external diameter 0.76mm of resulting oven dry, internal diameter 0.57mm, at absolute alcohol, soak after 10 minutes, with pure water, clean up again, obtain film silk pure water flux (interior pressure): 850L/m2h@0.1mPa, 25 ℃, the fracture tensile strength 4.3mPa of film silk, the compressive resistance of film silk (interior pressure) > 0.8mPa.Polyvinylpyrrolidone (PVP K10, molecular weight 10,000 dalton) rejection is 42%.In pure water, film silk soaks the COD content < 1ppm in water after 3 months.
Comparative example one
Adopt formula and the preparation method of embodiment mono-, difference is that the formula of macromolecule spinning casting solution is polyethersulfone resin (BASFE6020P, molecular weight 55,000 dalton) 17%, dimethylacetylamide (DMAC) 61%, polyvinyl pyridine alkane ketone (PVP K30) 8.5%, diethylene glycol (DEG) 13.5%.Spinning temperature maintains 50 ℃.
Inside and outside solidification liquid component is identical with embodiment mono-with spinning temperature.
The polyether sulphone hollow fibre film external diameter 0.74mm of resulting oven dry, internal diameter 0.52mm, after alcohol-pickled 10 minutes, with pure water, clean up again, obtain film silk pure water flux (interior pressure): 345L/m2h@0.1mPa, 25 ℃, the fracture tensile strength 4.3mPa of film silk, the compressive resistance of film silk (interior pressure) > 0.8mPa.Polyvinylpyrrolidone (PVP K10, molecular weight 10,000 dalton) rejection is 92%.In pure water, film silk soaks the COD content > 20ppm in water after 3 months.The cross section electron-microscope scanning figure of the PES of preparing for this comparative example as Fig. 3.
Its inside of filter membrane prepared by comparative example is coarse, and the organic substance residues in film is many, easily causes the pollution of filtration system.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.
Claims (9)
1. a PES, is characterized in that, described polyether sulfone preparation liquid is comprised of the component of following percetage by weight:
Polyethersulfone resin 15-20%,
Polar solvent 45-60%,
Polar micromolecules pore former 15-30%,
Inorganic solubility salt or hydrophobic oxide-based pore former 1-8%.
2. a PES, is characterized in that, described polyether sulfone preparation liquid is comprised of the component of following percetage by weight:
Polyethersulfone resin 20-30%,
Polar solvent 50-65%,
Polar micromolecules pore former 10-15%,
Inorganic solubility salt or hydrophobic oxide-based pore former 5-15%.
3. the PES as described in claim 1-2 any one, is characterized in that, described polar solvent is dimethylacetylamide, dimethyl formamide, 1-METHYLPYRROLIDONE or methyl-sulfoxide, described polar micromolecules pore former be water,
Ethanol, ethylene glycol, diethylene glycol, isopropyl alcohol, glycerine or butanols.
4. the PES as described in claim 1-2 any one, it is characterized in that, film silk external diameter 0.3-1.5mm, internal diameter 0.1-1.0mm, wall thickness 0.1-0.5mm, film surface apertures 0.003-0.5 μ m, molecular cut off is that 1000-20000 dalton reaches 0.5-100%, at 0.1MPa, under 25 degrees Celsius, inner pressed pure water flux is 50-1000L/m
2h, the stretch breaking strength of film silk is 3.0-6.0MPa, the compressive resistance > 0.8MPa of film silk soaks three months in water, measures the content < 1ppm of COD in water.
5. the non-solvent phase separation method preparation method of the PES described in claim 1 or 2, is characterized in that comprising the steps:
(1) according to the formula described in claim 1 or 2, take each component, each component is invested in spinning still, stirring and dissolving 8-10 hour at 75-95 ℃, makes the spinning casting solution mixing, and vacuum discontinuous degassing is also held in 80 ℃ of needed spinning temperature 25 –;
(2) use the non-solvent phase separation method technique spinning of dry-wet method: casting solution prepared by step (1) filters by the spinning of spray silk mould, spray the spun silk of silk mould coagulation forming in coagulating bath, make polyether sulphone hollow fibre film milipore filter crude product;
(3) the polyether sulphone hollow fibre film milipore filter crude product that prepared by step (2) soaks except the inorganic salts pore former in striping silk in rare inorganic acid, then with cleaning and remove residual organic solvent in 50-60 ℃ of water, finally, after soaking in ethanol and hexane solution successively, 60 ℃ of oven dry.
6. preparation method as claimed in claim 5, is characterized in that, described polar solvent is dimethylacetylamide, dimethyl formamide, 1-METHYLPYRROLIDONE or methyl-sulfoxide.
7. preparation method as claimed in claim 5, it is characterized in that, described polar micromolecules pore former is water, ethanol, ethylene glycol, diethylene glycol, isopropyl alcohol, glycerine or butanols, described inorganic solubility salt is lithium chloride, lithium nitrate, lithium perchlorate or nano-sized hydrophobic calcium carbonate, hydrophobic oxide-based be nano-sized hydrophobic zinc oxide or nano-sized hydrophobic zirconia.
8. preparation method as claimed in claim 5, is characterized in that, described inorganic acid is hydrochloric acid, sulfuric acid or nitric acid.
9. preparation method as claimed in claim 5, is characterized in that, described coagulating bath comprises outer solidification liquid and interior solidification liquid; Described outer solidification liquid is pure water, or the mixed liquor of pure water and ethanol, isopropyl alcohol or ethylene glycol, and the weight percentage of water is not less than 70%; Described interior solidification liquid is pure water, or the mixed liquor of pure water and polar solvent dimethylacetylamide, dimethyl formamide, methyl-sulfoxide or 1-METHYLPYRROLIDONE, and in described mixed liquor, the weight percent content of water is 40-80%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010278600.6A CN102397760B (en) | 2010-09-08 | 2010-09-08 | Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010278600.6A CN102397760B (en) | 2010-09-08 | 2010-09-08 | Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102397760A CN102397760A (en) | 2012-04-04 |
| CN102397760B true CN102397760B (en) | 2014-04-09 |
Family
ID=45880644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010278600.6A Active CN102397760B (en) | 2010-09-08 | 2010-09-08 | Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102397760B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102941027B (en) * | 2012-11-30 | 2014-11-19 | 艾特克控股集团有限公司 | Method for producing high-flux ultra-filtration membrane |
| CN103933866A (en) * | 2013-01-17 | 2014-07-23 | 华东理工大学 | Preparation method of hollow fiber 316L stainless steel membrane |
| CN104607058B (en) * | 2014-12-30 | 2017-06-23 | 武汉艾科滤膜技术有限公司 | A kind of production method of polyvinyl chloride hollow fiber microfiltration membranes |
| CN104785120A (en) * | 2015-03-25 | 2015-07-22 | 杭州汉膜新材料科技有限公司 | Noumenon hydrophilic hollow fiber membrane and preparation method thereof |
| CN104923093A (en) * | 2015-07-01 | 2015-09-23 | 芜湖市晨曦新型建材科技有限公司 | Hollow fiber ultrafiltration membrane of water purifier and preparation method for hollow fiber ultrafiltration membrane |
| CN107282140B (en) * | 2016-03-31 | 2019-11-19 | 华东理工大学 | A kind of perfluorinated sulfonic resin/PES/TiO2-ZrO2The preparation method of solid acid doughnut catalyst filling |
| CN106422796A (en) * | 2016-05-10 | 2017-02-22 | 广州康柏能量健康科技有限公司 | Filter membrane for resisting bacteria and eliminating nitrite and purification filter element thereof |
| JP6824284B2 (en) * | 2016-11-09 | 2021-02-03 | 旭化成株式会社 | Method for manufacturing porous hollow fiber membrane and porous hollow fiber membrane |
| CN110152505B (en) * | 2019-06-10 | 2020-08-25 | 泰州禾益新材料科技有限公司 | Preparation method of double-layer polysulfone hollow fiber ultrafiltration membrane |
| CN110330651B (en) * | 2019-06-12 | 2020-05-01 | 扬州清研高分子新材料有限公司 | Method for preparing polyether sulfone |
| CN112439324A (en) * | 2019-08-10 | 2021-03-05 | 杭州科百特过滤器材有限公司 | Preparation method of filtering membrane |
| CN112569813A (en) * | 2020-11-19 | 2021-03-30 | 厦门大学 | Preparation method of inorganic nano material reinforced hollow fiber ultrafiltration membrane |
| CN113457476A (en) * | 2021-07-08 | 2021-10-01 | 山东招金膜天股份有限公司 | Polysulfone hollow fiber membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005193194A (en) * | 2004-01-09 | 2005-07-21 | Kuraray Co Ltd | Polyphenyl sulfone porous membrane and its production method |
| 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 |
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| CN101396642A (en) * | 2008-10-24 | 2009-04-01 | 东华大学 | Antibiotic hollow fiber separation film and preparation method thereof |
-
2010
- 2010-09-08 CN CN201010278600.6A patent/CN102397760B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005193194A (en) * | 2004-01-09 | 2005-07-21 | Kuraray Co Ltd | Polyphenyl sulfone porous membrane and its production method |
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| 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 |
| CN101396642A (en) * | 2008-10-24 | 2009-04-01 | 东华大学 | Antibiotic hollow fiber separation film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 邓建绵等.聚砜中空纤维超滤基膜的制备.《信阳师范学院学报：自然科学版》.2009,第22卷(第4期),第572-576页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102397760A (en) | 2012-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102397760B (en) | Polyether sulfone hollow fiber ultrafiltration membrane and preparation method thereof | |
| CN104607064A (en) | Method for preparing polyvinylidene fluoride-graphene oxide composite hollow fiber membrane | |
| JP5293959B2 (en) | Hollow fiber membrane and method for producing the same | |
| CN102527250B (en) | Hollow fibrous membrane and preparation method thereof | |
| CN101396642B (en) | Antibiotic hollow fiber separation film and preparation method thereof | |
| CN105289319B (en) | A kind of preparation method of polymer hollow fiber membrane | |
| KR101494053B1 (en) | Method for manufacturing asymmetric hollow fiber membrane and asymmetric hollow fiber membrane manufactured using the same | |
| KR20080057637A (en) | Method for manufacturing polyvinylidene fluoride hollow fiber membrane and hollow fiber membrane | |
| CN101422706A (en) | Preparation method of co-mixing polyvinylidene fluoride hollow fiber membrane with improved hydrophilicity | |
| CN101596417B (en) | Preparation method of blended kynoar polyvinylidene fluoride hollow fabulous membrane for blood purification | |
| KR20130040620A (en) | Preparation method of hollow fiber membrane with high mechanical properties made of hydrophilic modified polyvinylidenefluoride for water treatment | |
| CN103894078A (en) | High-flux polyvinylidene fluoride hollow fiber film and preparation method thereof | |
| CN101596418B (en) | Preparation method of blended kynoar polyvinylidene fluoride hollow fabulous membrane for blood filtration | |
| CN101590376B (en) | Preparation of blending polyvinylidene fluoride hollow fiber membrane with improved dimensional stability | |
| CN109621741B (en) | Preparation method of forward osmosis composite membrane | |
| KR20070103187A (en) | Porous poly(vinylidene fluoride) hollow fiber membranes composed of both fibril and nodular structures | |
| JPS6138207B2 (en) | ||
| KR101568032B1 (en) | Method for Manufacturing Porous Membrane and Porous Membrane Manufactured thereby | |
| WO2018159353A1 (en) | Method for preparing polyphenylsulfone porous hollow fiber membrane | |
| CN107913604B (en) | Preparation method of PVDF/PVDF-HFP hollow fiber membrane | |
| JP2010082509A (en) | Porous membrane | |
| US20130313739A1 (en) | Membrane-forming dope solution for carbon membranes and method for producing carbon hollow fiber membranes using the same | |
| JPH05161833A (en) | Production of semipermeable membrane having high water permeability | |
| CN110721597B (en) | Method for simply preparing porous membrane with excellent connectivity | |
| KR20130040623A (en) | The preparation method of hollow fiber membrane with high permeation using hydrophilic polyvinylidenefluoride composites for water treatment |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20160918 Address after: Zhongguancun Pinggu Science Park, industrial park 101200 Beijing city Pinggu District 2 District No. 11 Patentee after: HUAWEI TECHNOLOGIES CO., LTD. Address before: 621000 Mianyang city of Sichuan Province Branch Park No. 249 Middle Road Patentee before: Mianyang Midea Material Technology Co.,Ltd. |