CN102219969A - Polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and thermally induced phase separation preparation method - Google Patents
Polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and thermally induced phase separation preparation method Download PDFInfo
- Publication number
- CN102219969A CN102219969A CN2010101509612A CN201010150961A CN102219969A CN 102219969 A CN102219969 A CN 102219969A CN 2010101509612 A CN2010101509612 A CN 2010101509612A CN 201010150961 A CN201010150961 A CN 201010150961A CN 102219969 A CN102219969 A CN 102219969A
- Authority
- CN
- China
- Prior art keywords
- pvdf
- polyethersulfone
- hollow
- polyvinylidene difluoride
- preparation
- 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.)
- Granted
Links
Abstract
The invention relates to a polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and a thermally induced phase separation preparation method thereof. Raw materials for preparing the polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane provided by the invention comprise a main material, and the main material is composed of polyvinylidene fluoride and polyether sulfone, wherein the weight ratio of the polyvinylidene fluoride to the polyether sulfone is 1.25-10. The hollow fiber member which is prepared by a thermally induced phase separation (TIPS) spinning technology has high strength, uniform pore size and uniform pore size distribution. The polyether sulfone (PES) is added into the polyvinylidene fluoride (PVDF); and the prepared polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane silk not only has the properties of the polyvinylidene fluoride material which has the advantages of good anti-chemical performance, good flexibility and the like, but also has the properties of the polyether sulfone material which has good hydrophilcity, rigidity and the like; and two materials can complement each other through blending so that the prepared hollow fiber membrane silk has a high water flux, and the compressive strength, tensile strength and pollution resistance of the membrane silk are greatly improved.
Description
Technical field
The present invention relates to a kind of polyvinylidene difluoride (PVDF)-polyethersulfone blended hollow-fibre membrane, with and the thermic preparation method that is separated.
Background technology
Ultra-filtration membrane is that a kind of pore diameter range is the micropore filtering film of 0.001-0.1 micron., low voltage operated based on the ultra-filtration membrane isolation technique (ultrafiltration) of ultra-filtration membrane with its normal temperature, no phase transformation, distinguishing feature such as energy consumption is low, become a kind of novel sepn process, be widely used in water treatment (as drink water purifying), beverage, biology, food, medicine and other fields.
The character of film properties and mould material is closely related.Polyvinylidene difluoride (PVDF) (PVDF) is a kind of crystal polymer thing, and fusing point is lower, melt fluidity good, can carry out molding, extrusion molding, injection moulding, blowing processing.Tensile strength height, good toughness, excellent in cushion effect, abrasion performance, anti-creep; Have higher thermotolerance, can be in-62 ℃～150 ℃ temperature ranges life-time service; Has outstanding weatherability, anti-ozone, ultraviolet resistance; Polyvinylidene difluoride (PVDF) (PVDF) has excellent chemical stability, is not corroded by acid, alkali, strong oxidizer and halogen under the room temperature, and common organic solvents does not have influence to it yet.Polyvinylidene difluoride (PVDF) (PVDF) over-all properties is good, is a kind of mould material of excellent performance, is widely used in the manufacturing of various separatory membranes.But the surface energy of polyvinylidene difluoride (PVDF) is extremely low, is the very strong material of a kind of hydrophobicity.
Polyethersulfone (PES) has excellent physical and mechanical properties, intensity height, good rigidly, and creep resistant is good, at high temperature uses continuously and still can keep stable performance in temperature environment jumpy.The polyethersulfone chemical proofing is good, under general acid, alkali, aliphatic hydrocarbon, grease, alcohols equal solvent condition, keep stable, at high temperature can be not by acid and alkali corrosion, can anti-gasoline, clean-out systems such as machine oil, lubricated wet goods oils and fluorine Lyons, it has anti-solvent cracking behavior best in the noncrystalline resin.The physical strength of polyether sulfone materials is better than polyvinylidene fluoride material, and the wetting ability of material itself is also good than polyvinylidene fluoride material, but the mechanical extensibility of its material is than polyvinylidene fluoride material difference.
Use polyvinylidene difluoride (PVDF) to prepare ultra-filtration membrane in the prior art, because polyvinylidene difluoride (PVDF) (PVDF) surface energy is low, has very strong hydrophobicity, so need in polyvinylidene difluoride (PVDF), add the hydrophilic modifying agent or with other hydrophilic polymer materials blend or surface modification, make the film silk in water, present wetting ability, the preparation method of film adopts non-solvent phase separation method (NIPS), disclose CN9511749T number as Chinese patent, the preparation of CN98103053 number and the described polyvinylidene fluoride (PVDF) ultrafiltration membrane of CN101439268A patent application, wherein CN9511749T number, the CN98103053 patent application is described with non-solvent phase separation method (NIPS) technology and system film formulation and is comprised a large amount of hydroaropic substances of adding, make the film silk in water, present polyvinylidene difluoride (PVDF) filter membrane that wetting ability and CN101439268A patent application preparation prepares with the non-solvent phase separation method by make polyvinylidene difluoride (PVDF) (PVDF) resin raw material formation active group with chemical treatment method, again with hydrophilic compounds methyl propenoic acid glycidyl alcohol or vinylformic acid reaction, hydrophilization polyvinylidene difluoride (PVDF) (PVDF) starting material that form modification are made, and its tensile strength is 1.3～3.5N, mean pore size is 0.05 μ m, flux is 900～1000L/m
2H.The bad mechanical strength and the shrinkability in the polyvinylidene fluoride material drying process of the polyvinylidene difluoride (PVDF) class hollow-fibre membrane made from non-solvent phase separation method technology (NIPS) are the weakness of the maximum of this class material membrane silk.
Chinese patent discloses CN 1014122706A number and has introduced a kind of non-solvent phase separation method (NIPS) its preparation process that improves hydrophilic blend polyvinylidene fluoride hollow-fibre membrane that has, in conjunction with two kinds of properties of materials, with polyvinylidene difluoride (PVDF), polyethersulfone, derivatived cellulose, pore former and solvent by weight percentage 8～25%, 1～8%, 0.1～10%, 1～15%, 70～90% mix, go out the blend polyvinylidene fluoride hollow-fibre membrane with dry-wet spinning non-solvent phase separation method (NIPS) prepared, adding a spot of polyethersulfone can make the shrinking percentage of film decline to a great extent, flux is improved, the physical strength of film silk is also improved, have anti-damage performance preferably.Zhi Bei blend polyvinylidene fluoride hollow-fibre membrane has increased pure polyvinylidene fluoride film hydrophilically and dimensional stability simultaneously.But adopt to do-wet method is the preparation of non-solvent phase separation method (NIPS) spinning technique, promptly use blend polyvinylidene fluoride (PVDF)/polyethersulfone (PES) prescription, the hollow-fibre membrane silk physical strength of this prepared is still low and not enough, pore size and skewness.In patent AU 653528, describe with thermally induced phase separation (TIPS) preparation hollow-fibre membrane, be with the polyvinylidene fluoride resin (PVDF) and the organic pore former that is mixed, under 220 ℃ of high temperature and partial vacuum, form molten materials, under 215 ℃, extrude tubular fibre by the slush molding nozzle then, form hollow-fibre membrane like this, but the membrane porosity that forms is low.In order to improve the problem that above-mentioned filming technology exists, a kind of manufacturing process with polyvinylidene fluoride resin (PVDF) tubular fibre porous-film of bigger physical strength and higher resistance to pressure is disclosed for Japanese kokai publication hei 3-215535 number, the inorganic nanometer powder that is mixed with phthalic acid n-octyl organic pore former such as (DOP) and water drain silica in polyvinylidene fluoride resin is as inorganic pore former, after melt extruding moulding under up to 250 ℃ of temperature, extract organic and inorganic pore former, obtain the symmetric membrane in the decorticate homogeneous of surfaces externally and internally aperture like this, but the filtering accuracy of this film greatly reduces, and voidage is also lower.
Summary of the invention
In order to overcome above-mentioned defective, the invention provides a kind of polyvinylidene difluoride (PVDF)-polyethersulfone blended hollow-fibre membrane.Blend is learnt from other's strong points to offset one's weaknesses the performance of the two, thereby prepared hollow-fibre membrane silk is except that having high water flux, improves resistance to compression and the tensile strength and the resistance to crocking of film silk widely.
Polyvinylidene difluoride (PVDF) of the present invention-polyethersulfone blended hollow-fibre membrane, its preparation raw material comprises material of main part, and described material of main part is made up of polyvinylidene difluoride (PVDF) and polyethersulfone, and wherein polyvinylidene difluoride (PVDF) is 1.25-10 with the ratio of the weight of polyethersulfone.Filter membrane of the present invention preferably comes by the thermally induced phase separation preparation.
Preferably, also comprise the component of following weight percentage in the described preparation raw material: polyvinylidene difluoride (PVDF) 25～50%, polyethersulfone 5～20%, thinner 20～40%, inorganic pore former 5～20%.
Preferably, described thinner is selected from one or more in o-phthalic acid dibutyl ester, dimixo-octyl phthalate, dibutyl phthalate, dimethyl phthalate, phthalic acid two isodecyl fat, Octyl adipate, clorafin and the soybean oil; Nano compound that described inorganic pore former is selected from hydrophobization is as one or more in lime carbonate, silicon-dioxide, zinc oxide, kaolin and the talcum powder.
Polyvinylidene difluoride (PVDF) of the present invention-polyethersulfone blended hollow-fibre membrane, its aperture are 0.01～0.1 μ m, and pure water flux is 500～2500L/m
2H (0.1MPa, 25 ℃), parting pressure＞0.8MPa, tensile strength 7～25MPa.)
The present invention also provides the thermic of a kind of polyvinylidene difluoride (PVDF)-polyethersulfone blended hollow-fibre membrane preparation method that is separated, comprise the steps: that (1) prepare the preparation raw material: material of main part, thinner and inorganic pore former are mixed and stir, wherein material of main part is made up of polyvinylidene difluoride (PVDF) and polyethersulfone, and wherein polyvinylidene difluoride (PVDF) is 1.25-10 with the ratio of the weight of polyethersulfone; (2) mixture with step (1) gained melt extrudes into hollow fiber in 200～320 ℃ twin screw extruder, enters cooling forming in 20～60 ℃ the tank then; (3) behind the tubular fibre process thinner extraction agent and extraction of inorganic pore former extraction agent and extraction with step (2) cooling forming, obtain polyvinylidene difluoride (PVDF)-polyethersulfone blended hollow-fibre membrane.
In a preferred embodiment of the present utility model, described preparation raw material comprises the component of following weight percentage: polyvinylidene difluoride (PVDF) 25～50%, polyethersulfone 5～20%, thinner 20～40%, inorganic pore former 5～20%.
Preferably, described thinner is selected from one or more in o-phthalic acid dibutyl ester, dimixo-octyl phthalate, dibutyl phthalate, dimethyl phthalate, phthalic acid two isodecyl fat, Octyl adipate, clorafin and the soybean oil; Nano compound that described inorganic pore former is selected from hydrophobization is as one or more in lime carbonate, silicon-dioxide, zinc oxide, kaolin and the talcum powder.
Preferably, the thinner extraction agent is selected from one or more in normal hexane, hexanaphthene, ethanol, gasoline and the methylene dichloride.
Preferably, inorganic pore former extraction agent is selected from one or more in sulfuric acid, hydrochloric acid, sodium hydroxide and the potassium hydroxide.
Preferably, the length-to-diameter ratio of described twin screw extruder is 20～40: 1.Thereby finished in the step that is molded in the twin screw extruder of the mixing and tubular fibre of material.Generally needing to avoid first mixing granulator, again two step processes of extruding spinning.
Employed polyvinylidene difluoride (PVDF) and polyethersulfone all are the extrusion grade resins among the present invention.
The thermally induced phase separation that relates among the present invention (TIPS) is a kind of method that begins to be used to prepare porous diffusion barrier early 1980s, it is to form homogeneous phase solution when the comparatively high temps by thermoplasticity and crystalline superpolymer and some high boiling micromolecular compound (thinner), solid-liquid or liquid-liquid phase separation take place when temperature reduces, and become the high polymer stephanoporate film after removing thinner.This method that is separated by the temperature change driving is called thermally induced phase separation.
The present invention adopts thermally induced phase separation (TIPS) spinning technique, compare than traditional non-solvent phase separation method (NIPS) spinning technique, the tubular fibre film toughness height of thermally induced phase separation (TIPS) preparation, pore size evenly, even aperture distribution, and avoid fully because the immiscible property of the material of polyvinylidene difluoride (PVDF) (PVDF) and polyethersulfone (PES) also causes the unstable of the solution that may occur when preparing macromolecular solution.In polyvinylidene difluoride (PVDF) (PVDF), add polyethersulfone (PES), increased the wetting ability of polyvinylidene fluoride film, improved the resistance to compression and the tensile strength of hollow-fibre membrane.Polyvinylidene difluoride (PVDF) (PVDF)/polyethersulfone (PES) the alloy hollow-fibre membrane of the present invention's preparation has more outstanding performance: its aperture is 0.01～0.1 μ m, and pure water flux is 500～2500L/m
2H (0.1MPa, 25 ℃), parting pressure＞0.8MPa, tensile strength are 7～25MPa.
Embodiment
Embodiment 1
Take by weighing 45% polyvinylidene difluoride (PVDF) (PVDF), 5% polyethersulfone (PES), 20% o-phthalic acid dibutyl ester, 15% Octyl adipate, 15% hydrophobization nano zine oxide (particle diameter＜40nm) stir by weight with homogenizer, the material that stirs is through 280 ℃ twin screw extruder fusion plastification, through the telescoping spinning nozzle, the spinning nozzle pipe core feeds nitrogen, be extruded into hollow fiber, air distance through 5cm enters 40 ℃ of tank cooling formings then, and the tubular fibre after the moulding is collected with wire wrapping wheel.Tubular fibre after the collection extracts thinner o-phthalic acid dibutyl ester, Octyl adipate and inorganic pore former zinc oxide and extract with normal hexane and sulfuric acid respectively, make the external diameter 1.24mm of polyvinylidene fluoride/polyethersulfone sulfone alloy hollow-fibre membrane, internal diameter 0.65mm, voidage 77%, bubbling pressure is 0.27MPa, pure water flux is 1,685L/m
2H (0.1MPa, 25 ℃), parting pressure＞0.8MPa, tensile break strength 19.7MPa, tension fracture elongation are 120%, the water contact angle of film outer surface is 58 °.
Embodiment 2
Adopt embodiment 1 preparation method and technology, difference takes by weighing 40% polyvinylidene difluoride (PVDF), 10% polyethersulfone, 20% phthalic acid Diisooctyl, 10% dimethyl phthalate, 10% lime carbonate, 10% hydrophobization nano-calcium carbonate (particle diameter＜60nm) stir with homogenizer by weight at prescription, the material that stirs is through 302 ℃ twin screw extruder fusion plastification, 20 ℃ of tank cooling formings, spinning technique is identical with embodiment 1.Tubular fibre after the moulding is collected with wire wrapping wheel.Tubular fibre after the collection extracts thinner phthalic acid Diisooctyl, dimethyl phthalate and inorganic pore former lime carbonate and extract with hexanaphthene and hydrochloric acid respectively, the polyvinylidene fluoride/polyethersulfone sulfone alloy hollow-fibre membrane external diameter 1.23mm that makes, internal diameter 0.64mm, voidage 73%, bubbling pressure is 0.30MPa, pure water flux is 1,285L/m
2H (0.1MPa, 25 ℃), parting pressure＞0.8MPa, tensile break strength are that 21.6MPa, tension fracture elongation are 110%, and the water contact angle of film outer surface is 54 °.
Embodiment 3
Adopt embodiment 1 preparation method and technology, difference takes by weighing 35% polyvinylidene difluoride (PVDF), 10% polyethersulfone, 20% dimixo-octyl phthalate, 15% dimethyl phthalate, 20% hydrophobization nano zine oxide (particle diameter＜40nm) stir with homogenizer by weight at prescription, the material that stirs is through 310 ℃ twin screw extruder fusion plastification, through 60 ℃ tank cooling forming, spinning technique is identical with embodiment 1.The polyvinylidene difluoride (PVDF) that makes (PVDF)/polyethersulfone (PES) alloy hollow-fibre membrane external diameter 1.23mm, internal diameter 0.64mm, voidage 73%, bubbling pressure is 0.30MPa, pure water flux is 1,185L/m
2H (0.1MPa, 25 ℃), parting pressure＞0.8MPa, tensile break strength are that 21.6MPa, tension fracture elongation are 110%, and the water contact angle of film outer surface is 61 °.
Embodiment 4
Adopt embodiment 1 preparation method and technology, difference takes by weighing 30% polyvinylidene difluoride (PVDF), 20% polyethersulfone, 25% dimixo-octyl phthalate, 10% dibutyl phthalate, 15% water drain silica (particle diameter＜20nm) stir with homogenizer by weight at prescription, the material that stirs is through 315 ℃ twin screw extruder fusion, 50 ℃ of tank cooling plasticizing formings, spinning technique is identical with embodiment 1.Tubular fibre spinning after the collection extracts thinner dimixo-octyl phthalate, dibutyl phthalate and inorganic pore former silicon-dioxide and extract with methylene dichloride, ethanol and sodium hydroxide solution respectively.The hollow-fibre membrane external diameter 1.23mm that makes, internal diameter 0.64mm, voidage 73%, bubbling pressure is 0.33MPa, pure water flux is 985L/m
2H (0.1MPa, 25 ℃), parting pressure＞0.8MPa, tensile break strength are that 23.3MPa, tension fracture elongation are 92%, and the water contact angle of film outer surface is 60.3 °.
Embodiment 5
Adopt embodiment 1 preparation method and technology, difference takes by weighing 25% polyvinylidene difluoride (PVDF), 20% polyethersulfone, 15% Di Iso Decyl Phthalate, 10% dibutyl phthalate, 10% soybean oil, 5% water drain silica (particle diameter＜20nm), 15% hydrophobization zinc oxide (particle diameter＜40nm) stir with homogenizer by weight at prescription, the material that stirs is through 290 ℃ twin screw extruder fusion, 35 ℃ of tank cooling plasticizing formings, spinning technique is identical with embodiment 1.Tubular fibre spinning after the collection extracts thinner Di Iso Decyl Phthalate, dibutyl phthalate, soybean oil and inorganic pore former water drain silica, zinc oxide and extract with methylene dichloride, ethanol and sodium hydroxide solution, hydrochloric acid soln respectively.The hollow-fibre membrane external diameter 1.24mm that makes, internal diameter 0.64mm, voidage 78%, bubbling pressure is 0.32MPa, pure water flux is 1,879L/m
2H (0.1MPa, 25 ℃), parting pressure＞0.8MPa, tensile break strength are that 18.2MPa, tension fracture elongation are 90%, and the water contact angle of film outer surface is 58.3 °.
Comparing embodiment
Just in prescription, do not add polyethersulfone (PES), take by weighing 45% polyvinylidene difluoride (PVDF) (PVDF), 21% o-phthalic acid dibutyl ester, 17% Octyl adipate, 17% hydrophobization nano zine oxide (particle diameter＜40nm) stir by weight with homogenizer, the material that stirs is through 240 ℃ twin screw extruder fusion plastification moulding, and spinning technique is identical with embodiment 1.Pure polyvinylidene difluoride (PVDF) (PVDF) the hollow-fibre membrane external diameter 1.26mm that makes, internal diameter 0.68mm, voidage 79%, bubbling pressure is 0.22MPa, pure water flux is 1,985L/m
2H (0.1MPa, 25 ℃), parting pressure＞0.6MPa, tensile break strength are that 9.6MPa, tension fracture elongation are 150%, and the water contact angle of film outer surface is 87 °.
Can analyze by comparing embodiment and to obtain: not use polyethersulfone in the preparation raw material among the comparative example, only use polyvinylidene difluoride (PVDF), also adopt the thermic phase disengagement method to prepare hollow-fibre membrane, but its bubbling pressure of hollow-fibre membrane and the tensile break strength prepared obviously reduce.Proof only uses the big and tension physical strength in the aperture on its film surface of film that polyvinylidene difluoride (PVDF) prepares and survivability relatively poor.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. polyvinylidene difluoride (PVDF)-polyethersulfone blended hollow-fibre membrane, its preparation raw material comprises material of main part, it is characterized in that described material of main part is made up of polyvinylidene difluoride (PVDF) and polyethersulfone, and wherein polyvinylidene difluoride (PVDF) is 1.25-10 with the ratio of the weight of polyethersulfone.
2. hollow-fibre membrane as claimed in claim 1 is characterized in that, also comprises thinner and inorganic pore former in the described preparation raw material, and described preparation raw material comprises the component of following weight percentage:
Polyvinylidene difluoride (PVDF) 25～50%, polyethersulfone 5～20%,
Thinner 20～40%, inorganic pore former 5～20%.
3. hollow-fibre membrane as claimed in claim 1 or 2 is characterized in that, described polyvinylidene difluoride (PVDF) and polyethersulfone all are the extrusion grade resin.
4. hollow-fibre membrane as claimed in claim 2, it is characterized in that described thinner is selected from one or more in o-phthalic acid dibutyl ester, dimixo-octyl phthalate, dibutyl phthalate, dimethyl phthalate, phthalic acid two isodecyl fat, Octyl adipate, clorafin and the soybean oil; Nano compound that described inorganic pore former is selected from hydrophobization is as one or more in lime carbonate, silicon-dioxide, zinc oxide, kaolin and the talcum powder.
5. as claim 1 or 4 described hollow-fibre membranes, it is characterized in that described hollow-fibre membrane comes by the thermally induced phase separation preparation.
6. hollow-fibre membrane as claimed in claim 5 is characterized in that, the aperture of described hollow-fibre membrane is 0.01～0.1 μ m, pure water flux at 0.1MPa, 25 ℃ the time is 500～2500L/M
2H, parting pressure are 7～25MPa greater than 0.8Mpa and tensile strength.
7. the thermic of the polyvinylidene difluoride (PVDF)-polyethersulfone blended hollow-fibre membrane preparation method that is separated is characterized in that described method comprises the steps:
(1) prepare the preparation raw material: material of main part, thinner and inorganic pore former are mixed and stir, wherein said material of main part is made up of polyvinylidene difluoride (PVDF) and polyethersulfone, and wherein polyvinylidene difluoride (PVDF) is 1.25-10 with the ratio of the weight of polyethersulfone;
(2) mixture with step (1) gained melt extrudes into hollow fiber in 200～320 ℃ twin screw extruder, enters cooling forming in 20～60 ℃ the tank then;
(3) after the extraction and extraction of tubular fibre with step (2) cooling forming, obtain polyvinylidene difluoride (PVDF)-polyethersulfone blended hollow-fibre membrane through thinner extraction agent and inorganic pore former extraction agent.
8. preparation method as claimed in claim 7 is characterized in that, described preparation raw material comprises the component of following weight percentage:
Polyvinylidene difluoride (PVDF) 25～50%, polyethersulfone 5～20%,
Thinner 20～40%, inorganic pore former 5～20%.
9. preparation method as claimed in claim 7, it is characterized in that described thinner is selected from one or more in o-phthalic acid dibutyl ester, dimixo-octyl phthalate, dibutyl phthalate, dimethyl phthalate, phthalic acid two isodecyl fat, Octyl adipate, clorafin and the soybean oil; Nano compound that described inorganic pore former is selected from hydrophobization is as one or more in lime carbonate, silicon-dioxide, zinc oxide, kaolin and the talcum powder.
10. preparation method as claimed in claim 7 is characterized in that the thinner extraction agent is selected from one or more in normal hexane, hexanaphthene, ethanol, gasoline and the methylene dichloride.
11. preparation method as claimed in claim 7 is characterized in that, inorganic pore former extraction agent is selected from one or more in sulfuric acid, hydrochloric acid, sodium hydroxide and the potassium hydroxide.
12. preparation method as claimed in claim 7 is characterized in that, the length-to-diameter ratio of described twin screw extruder is 20～40: 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010150961 CN102219969B (en) | 2010-04-13 | 2010-04-13 | Polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and thermally induced phase separation preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010150961 CN102219969B (en) | 2010-04-13 | 2010-04-13 | Polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and thermally induced phase separation preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102219969A true CN102219969A (en) | 2011-10-19 |
| CN102219969B CN102219969B (en) | 2013-06-19 |
Family
ID=44776688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010150961 Active CN102219969B (en) | 2010-04-13 | 2010-04-13 | Polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and thermally induced phase separation preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102219969B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512970A (en) * | 2011-12-05 | 2012-06-27 | 天津工业大学 | Preparation method of polyvinylidene fluoride blending porous diaphragms and product thereof |
| CN103406032A (en) * | 2013-07-26 | 2013-11-27 | 东华大学 | Polyvinyl chloride/sulfonated polyether sulfone blended film and preparation method thereof |
| CN103981635A (en) * | 2014-05-09 | 2014-08-13 | 浙江省纺织测试研究院 | Preparation method of porous fiber non-woven fabric |
| CN104226129A (en) * | 2014-09-18 | 2014-12-24 | 四川大学 | Polyarylenesulfidesulfone hollow fiber and flat plate separating membrane and preparation method thereof |
| CN104968422A (en) * | 2013-03-21 | 2015-10-07 | 旭化成化学株式会社 | Multiporous hollow-fiber membrane and process for producing multiporous hollow-fiber membrane |
| CN106268356A (en) * | 2015-05-20 | 2017-01-04 | 宁波大学 | A kind of Thermal inactive prepares the method for ultra-high molecular weight polyethylene composite hollow fibre |
| CN107866155A (en) * | 2016-09-26 | 2018-04-03 | 天津工业大学 | A kind of method that polymer matrix MOFs hollow fiber ultrafiltration membranes are prepared using thermally induced phase separation |
| CN108654379A (en) * | 2018-05-07 | 2018-10-16 | 宁波大学 | Porous support layer and its preparation method methods and applications |
| CN108939947A (en) * | 2018-08-06 | 2018-12-07 | 天津工业大学 | Kynoar and ultra-high molecular weight polyethylene blending microporous membrane and preparation method thereof |
| CN110201558A (en) * | 2019-06-04 | 2019-09-06 | 泉州碧蓝膜科技有限责任公司 | A kind of reinforced PVDF of big flux not belt material ultrafiltration membrane and preparation method thereof |
| CN110331464A (en) * | 2019-06-28 | 2019-10-15 | 上海建沪鸿达科技有限公司 | A kind of dissolvant type nanofiber with very high performance |
| CN110964271A (en) * | 2019-11-27 | 2020-04-07 | 厦门江天智能仿生科技有限公司 | Composite membrane and preparation method and preparation equipment thereof |
| CN112755793A (en) * | 2020-12-31 | 2021-05-07 | 浙江工业大学 | Hydrophobic modified black talc-based composite pervaporation membrane and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1765981A (en) * | 2005-11-25 | 2006-05-03 | 东华大学 | Polyvinylidene fluoride and polyethersulfone blending membrane, production method and uses |
| 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 |
| CN101362057A (en) * | 2008-01-30 | 2009-02-11 | 清华大学 | Method for preparing polyvinylidene fluoride porous membrane |
| CN101396641A (en) * | 2008-10-31 | 2009-04-01 | 孟广祯 | Composite thermotropic phase separation film-making method |
| WO2009050850A1 (en) * | 2007-10-19 | 2009-04-23 | Kawasaki Jukogyo Kabushiki Kaisha | Separation membrane comprising polyethersulfone, process for production thereof, and stock solution for production of film |
| CN101422706A (en) * | 2008-11-18 | 2009-05-06 | 东华大学 | Preparation method of co-mixing polyvinylidene fluoride hollow fiber membrane with improved hydrophilicity |
-
2010
- 2010-04-13 CN CN 201010150961 patent/CN102219969B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1899678A (en) * | 2005-07-19 | 2007-01-24 | 天津工业大学 | Method for producing hollow fiber film |
| CN1765981A (en) * | 2005-11-25 | 2006-05-03 | 东华大学 | Polyvinylidene fluoride and polyethersulfone blending membrane, production method and uses |
| 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 |
| WO2009050850A1 (en) * | 2007-10-19 | 2009-04-23 | Kawasaki Jukogyo Kabushiki Kaisha | Separation membrane comprising polyethersulfone, process for production thereof, and stock solution for production of film |
| CN101362057A (en) * | 2008-01-30 | 2009-02-11 | 清华大学 | Method for preparing polyvinylidene fluoride porous membrane |
| CN101396641A (en) * | 2008-10-31 | 2009-04-01 | 孟广祯 | Composite thermotropic phase separation film-making method |
| CN101422706A (en) * | 2008-11-18 | 2009-05-06 | 东华大学 | Preparation method of co-mixing polyvinylidene fluoride hollow fiber membrane with improved hydrophilicity |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102512970A (en) * | 2011-12-05 | 2012-06-27 | 天津工业大学 | Preparation method of polyvinylidene fluoride blending porous diaphragms and product thereof |
| CN104968422B (en) * | 2013-03-21 | 2018-07-13 | 旭化成株式会社 | The manufacturing method of porous hollow fibres film and porous hollow fibres film |
| US10023709B2 (en) | 2013-03-21 | 2018-07-17 | Asahi Kasei Chemicals Corporation | Multiporous hollow-fiber membrane and process for producing multiporous hollow-fiber membrane |
| CN104968422A (en) * | 2013-03-21 | 2015-10-07 | 旭化成化学株式会社 | Multiporous hollow-fiber membrane and process for producing multiporous hollow-fiber membrane |
| CN103406032A (en) * | 2013-07-26 | 2013-11-27 | 东华大学 | Polyvinyl chloride/sulfonated polyether sulfone blended film and preparation method thereof |
| CN103406032B (en) * | 2013-07-26 | 2015-12-02 | 东华大学 | A kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane and preparation method thereof |
| CN103981635A (en) * | 2014-05-09 | 2014-08-13 | 浙江省纺织测试研究院 | Preparation method of porous fiber non-woven fabric |
| CN104226129A (en) * | 2014-09-18 | 2014-12-24 | 四川大学 | Polyarylenesulfidesulfone hollow fiber and flat plate separating membrane and preparation method thereof |
| CN106268356A (en) * | 2015-05-20 | 2017-01-04 | 宁波大学 | A kind of Thermal inactive prepares the method for ultra-high molecular weight polyethylene composite hollow fibre |
| CN107866155A (en) * | 2016-09-26 | 2018-04-03 | 天津工业大学 | A kind of method that polymer matrix MOFs hollow fiber ultrafiltration membranes are prepared using thermally induced phase separation |
| CN108654379A (en) * | 2018-05-07 | 2018-10-16 | 宁波大学 | Porous support layer and its preparation method methods and applications |
| CN108939947A (en) * | 2018-08-06 | 2018-12-07 | 天津工业大学 | Kynoar and ultra-high molecular weight polyethylene blending microporous membrane and preparation method thereof |
| CN108939947B (en) * | 2018-08-06 | 2020-12-04 | 天津工业大学 | Polyvinylidene fluoride and ultra-high molecular weight polyethylene blended microporous membrane and preparation method thereof |
| CN110201558A (en) * | 2019-06-04 | 2019-09-06 | 泉州碧蓝膜科技有限责任公司 | A kind of reinforced PVDF of big flux not belt material ultrafiltration membrane and preparation method thereof |
| CN110201558B (en) * | 2019-06-04 | 2021-11-09 | 泉州碧蓝膜科技有限责任公司 | Large-flux reinforced PVDF unlined ultrafiltration membrane and preparation method thereof |
| CN110331464A (en) * | 2019-06-28 | 2019-10-15 | 上海建沪鸿达科技有限公司 | A kind of dissolvant type nanofiber with very high performance |
| CN110964271A (en) * | 2019-11-27 | 2020-04-07 | 厦门江天智能仿生科技有限公司 | Composite membrane and preparation method and preparation equipment thereof |
| CN112755793B (en) * | 2020-12-31 | 2022-05-24 | 浙江工业大学 | Hydrophobic modified black talc-based composite pervaporation membrane and application thereof |
| CN112755793A (en) * | 2020-12-31 | 2021-05-07 | 浙江工业大学 | Hydrophobic modified black talc-based composite pervaporation membrane and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102219969B (en) | 2013-06-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102219969B (en) | Polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and thermally induced phase separation preparation method | |
| CN100579638C (en) | Modified polyvinyl chloride hollow fiber microporous memebrane and method for preparing the same | |
| CN102000515B (en) | Thermoplastic polyurethane hollow fiber membrane and preparation method thereof | |
| JPH03215535A (en) | Porous polyvinylidene fluoride film and production thereof | |
| CN101590374A (en) | A kind of Kynoar hollow-fibre membrane and preparation method thereof | |
| JP2010513590A (en) | Method for producing polyolefin microporous membrane by efficient extrusion | |
| CN110964271A (en) | Composite membrane and preparation method and preparation equipment thereof | |
| CN102580553A (en) | Method for manufacturing environmental-friendly hollow-fibre membrane | |
| KR101913178B1 (en) | Method for manufacturing of ceramic hollow fiber membrane and the ceramic hollow fiber membrane thereby | |
| CN101485961A (en) | Method for preparing polyvinylidene fluoride hollow fiber alloy film | |
| KR20160079271A (en) | polyvinylidene fluoride hollow fiber membrane and manufacturing method thereof | |
| KR20080057637A (en) | Method for manufacturing polyvinylidene fluoride hollow fiber membrane and hollow fiber membrane | |
| CN102397759B (en) | Polyether sulfone hollow fiber filter membrane and its preparation method | |
| KR101381080B1 (en) | Double layer hydrophilic hollow fiber membrane and its manufacturing method combined supported layer by Thermally Induced Phase Separation and active layer by Non-solvent Induced Phase Separation | |
| CN101961611B (en) | Hollow polyester fiber microporous membrane and preparation method thereof | |
| CN101890303B (en) | Hollow fibrous membrane with asymmetrical structure and preparation method thereof | |
| KR20160081612A (en) | PVDF porous hollow fiber membrane and the preparing method thereof | |
| CN103537203B (en) | A kind of Thermal inactive Pvdf Microporous Hollow Fiber Membrane and preparation method thereof | |
| CN101890309B (en) | Method for preparing hollow fiber membranes by using thermally induced phase separation (TIPS) process | |
| CN101879417B (en) | Hollow fiber membrane containing PMMA (Polymethyl Methacrylate) and preparation method thereof | |
| KR20170081001A (en) | Method for manufacturing of ceramic hollow fiber membrane and the ceramic hollow fiber membrane thereby | |
| KR101434166B1 (en) | Manufacturing method of highly efficient hollow fiber membranes and poor solvent for manufacturing hollow fiber | |
| KR101474728B1 (en) | Manufacturing method of polyvinylidene fluoride hollow fiber membrane with high strength | |
| CN101920173B (en) | Ultrafiltration membrane using ethylene glycol carbonic ester and diethylene glycol as diluent and manufacturing method thereof | |
| CN103638830A (en) | Preparation method of hot-method polyvinylidene fluoride hollow fiber membrane for drinking 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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220128 Address after: 226372 No. 5, Poyanghu Road, Sutong science and Technology Industrial Park, Nantong City, Jiangsu Province Patentee after: JIANGSU MEINENG FILM MATERIAL TECHNOLOGY CO.,LTD. Address before: 510660 first floor, building 7, Huangzhou Industrial Zone, chepo Road, Tianhe District, Guangzhou, Guangdong Patentee before: MEMSTAR (GUANGZHOU) Co.,Ltd. |
|
| TR01 | Transfer of patent right |