CN101884878A - Hollow fiber porous membrane in perfluoro polymer and preparation method thereof - Google Patents
Hollow fiber porous membrane in perfluoro polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a hollow fiber porous membrane in a perfluoro polymer and a preparation method thereof. A membrane forming system of the membrane comprises the following components in percentage by weight: 40 to 60 percent of perfluoro polymer; 10 to 30 percent of polymer additive, 10 to 30 percent of composite pore-forming agent and 5 to 20 percent of organic low-molecular liquid; the perfluoro polymer is a copolymerized modified product of tetrafluoroethylene and a perfluoro second monomer; the polymer additive is fluor alkaline-containing polymers or a mixture thereof; the composite pore-forming agent comprises a soluble pore-forming agent and a non-soluble pore-forming agent; and the organic low-molecular liquid is a diluent of the polymer additive with a high boiling point. The preparation method comprises the following steps of: forcibly mixing the polymer additive, the composite pore-forming agent and the organic low-molecular liquid; uniformly mixing the mixture and the perfluoro polymer particles; and injecting the mixture into a double-screw machine, performing melt blended spinning at a temperature of between 300 and 360 DEG C and finally performing a conventional post-processing to obtain the hollow fiber porous membrane.
Description
Technical field
The present invention relates to the membrane technology field, be specially a kind of (per) fluoropolymer doughnut perforated membrane and preparation method thereof.
Background technology
The (per) fluoropolymer materials that main chain is made up of carbon and fluorine, not only have excellent specific properties such as the outstanding corrosion resistance of polytetrafluoroethylene (PTFE), hear resistance, non-stickiness, coefficient of friction are low, resistance to weathering, and can process by conventional smelting process, therefore with it as extraordinary filter fiber, tubing liner, optical cable crust etc., be widely used in various fields such as chemical industry, machinery, electrical equipment.
The chemical stability that (per) fluoropolymer is given prominence to, good high temperature performance receive film researcher's concern day by day, and especially its good anti-corrosion makes it separate as the particulate that filtering material is widely used under the harsh conditions.The strong-hydrophobicity of (per) fluoropolymer makes it become the desirable membrane material of preparation waterproof and breathable, film distillation (MD), osmotic distillation (OD) and membrane contactor (MC) simultaneously.Identical with polytetrafluoroethylene (PTFE), the solvent that the chemical stability of (per) fluoropolymer excellence also makes nothing be fit to can be with its dissolving or with its dilution.Because the higher selection that has limited the pore-foaming agent in film-forming process of processing temperature of (per) fluoropolymer, therefore it is difficult to picture polysulfones, polyether sulfone or Kynoar adopt phase inversion like that or as polypropylene, polyethylene by the industrial doughnut membrane material of thermally induced phase separation preparation becoming.Therefore, less relatively about (per) fluoropolymer both at home and abroad as the patent documentation report of film forming polymer, United States Patent (USP) [LarryY.Yen, Tewksbury; GeorgeLopatin, FluorocarbonMembranesandProcessforMakingFluorocarbonMemb ranes, U.S.Patent (1990) 4902456] with the (per) fluoropolymer polymeric matrix, with CTFE oil (CTFE) is diluent, adopts thermic phase legal system to be equipped with the (per) fluoropolymer hollow-fibre membrane.U.S. duPont company carries out chlorination to improve its solvability in the halocarbon solvent to monomer in the (per) fluoropolymer polymerization process, the CTFE monomer of perhaps introducing gas phase in the spinning process of (per) fluoropolymer carries out spinning and prepares hollow-fibre membrane [RichardA.Morgan, Vienna, W.Va.WilliamH.Tuminello, Low-meltingtetrafluoroethyleneCopolymerandItsUses, U.S.Patent (1995) 5397829].But the cost price of said method is too high, has limited the large-scale industrial production of (per) fluoropolymer hollow-fibre membrane.Therefore, the industrialized process for preparing of exploitation (per) fluoropolymer doughnut perforated membrane is significant.
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Summary of the invention
At the deficiencies in the prior art, the technical problem that quasi-solution of the present invention is determined is that a kind of (per) fluoropolymer doughnut perforated membrane and preparation method thereof is provided.It is simple relatively that this film and preparation method have preparation technology, and processing cost is lower, and membrane aperture is controlled, and production efficiency is higher, saves the energy, is suitable for advantages such as industrializing implementation.
The technical scheme that the present invention solve the technical problem is: design a kind of (per) fluoropolymer doughnut perforated membrane, the film forming system percentage by weight of this film consists of:
(per) fluoropolymer 40 ~ 60;
Polymeric additive 10 ~ 30;
Composite pore-forming 10 ~ 30;
Organic low molecular liquid 5 ~ 20, each component sum is 100%,
Wherein, described (per) fluoropolymer is tetrafluoroethene base and the perfluor second monomer copolymerization modified product, comprise perfluoroethylene-propylene, tetrafluoroethene-perfluoro propyl vinyl ether, or the blend of perfluoroethylene-propylene and tetrafluoroethene-perfluoro propyl vinyl ether arbitrary proportion, described perfluor second monomer is hexafluoropropene, perfluoroalkyl vinyl ether or ethene; Described polymeric additive is the mixture of fluorine-containing alkane polymer or fluorine-containing alkane polymer, comprises Kynoar or polytrifluorochloroethylene; Described composite pore-forming comprises solubility pore-foaming agent and non-dissolubility pore-foaming agent, and the solubility pore-foaming agent is meant water-soluble substances, comprises the mixture of water-soluble inorganic particle, water-soluble polymer or water-soluble inorganic particle and water-soluble polymer arbitrary proportion; Described water-soluble inorganic particle comprises LiCl, the CaCl of average grain diameter 0.01-5 μ m
2, among NaCl and the KCl any one; Described water-soluble polymer is meant that decomposition temperature is higher than the water-soluble polymer of its spinning processing temperature, comprises polyoxyethylene; Described non-dissolubility pore-foaming agent is meant water-insoluble inorganic particulate, comprises that average grain diameter is the SiO of 0.01-5 μ m
2Or CaCO
3In a kind of, perhaps SiO
2And CaCO
3The mixture of arbitrary proportion; Described organic low molecular liquid is the diluent of high boiling polymeric additive, comprises a kind of in dioctyl phthalate or the dibutyl phthalate or the mixture of dioctyl phthalate and dibutyl phthalate arbitrary proportion.
The technical scheme that the present invention solves described preparation method's technical problem is: the preparation method who designs a kind of (per) fluoropolymer doughnut perforated membrane, the technology that this preparation method adopts is: earlier the film forming system is formed described polymeric additive, composite pore-forming and organic low molecular liquid and pour Forced Mixing in the mixing kettle into, form mixture of viscous form; Again mixture and resin particle are mixed; then the thing that is mixed is injected double screw extruder; under 300 ~ 360 ℃ of temperature; carry out the melt blending spinning through hollow-fiber module; the nascent film of preparation doughnut; wash through the water collection of conventional soln spinning at last and the after-drawing operation after, promptly obtain (per) fluoropolymer hollow-fibre membrane of the present invention.
Compared with prior art, the present invention is a kind of technology of preparing of brand-new (per) fluoropolymer (polytetrafluoroethylene (PTFE)) hollow-fibre membrane, designed heterogeneous film forming system is formed, can effectively reduce the melt processing temperature of (per) fluoropolymer, melt extrude temperature usually about 380 ℃ as conventional (per) fluoropolymer, and hollow-fibre membrane melt-spinning technology temperature of the present invention only requires 300 ~ 360 ℃, save a large amount of energy, simultaneously also reduced the melt spinning fluid viscosity, improved its flowability, thus the present invention to have technology simple relatively, spinning line is short, the preparation efficiency height, membrane aperture is controlled, is suitable for characteristics such as industrializing implementation.
The specific embodiment:
Below in conjunction with the further concrete narration the present invention of embodiment.
The (per) fluoropolymer doughnut perforated membrane (abbreviation hollow membrane) of the present invention's design, its film forming system mass percent prescription are formed:
(per) fluoropolymer 40 ~ 60;
Polymeric additive 10 ~ 20;
Composite pore-forming 20 ~ 40;
Organic low molecular liquid 5 ~ 20, each component sum is 100%.
During prescription of the present invention was formed, (per) fluoropolymer was basal lamina material or matrix phase.Described (per) fluoropolymer is tetrafluoroethene base and perfluor second monomer (hexafluoropropene, perfluoroalkyl vinyl ether, ethene etc.) modification by copolymerization body, comprises perfluoroethylene-propylene (FEP), tetrafluoroethene-perfluoro propyl vinyl ether (PFA) or its blend etc.Wherein the introducing of second monomer has destroyed the original regularity of molecular structure of polytetrafluoroethylene (PTFE), has reduced crystallinity of polymer, and the fusing point of copolymer reduces along with the increase of second content of monomer in the copolymer.Select for use other every physical and chemical index of (per) fluoropolymer should reach the fibre-grade level.
During hollow membrane prescription of the present invention is formed, described polymeric additive is fluorine-containing alkane polymer or its mixture more approaching with the (per) fluoropolymer solubility parameter, and requiring its decomposition temperature to be higher than the spinning processing temperature, melt viscosity and (per) fluoropolymer are close.Particularly, described polymeric additive comprises Kynoar (PVDF), polytrifluorochloroethylene (PCTFE) or its mixture etc.For the present invention, along with the increase of polymeric additive addition, the spinnability of film forming system is on a declining curve." fiber " co-extrusion takes place between (per) fluoropolymer and the polymeric additive because the low-surface-energy of (per) fluoropolymer, excessive polymeric additive make, make doughnut at fiber axis to cracking defective.Therefore the mass percent component of polymeric additive should be controlled at 10 ~ 20%.
During hollow membrane prescription of the present invention was formed, described composite pore-forming required decomposition temperature to be higher than spinning temperature.Particularly, described composite pore-forming is solubility pore-foaming agent and non-dissolubility pore-foaming agent, and the solubility pore-foaming agent is meant water-soluble substances, comprises the mixture of water-soluble inorganic particle, water-soluble polymer and water-soluble substances arbitrary proportion.Described water-soluble inorganic particle comprises LiCl, the CaCl of average grain diameter 0.01 ~ 5 μ m
2, a kind of among NaCl and KCl etc.; Described water-soluble polymer decomposition temperature is higher than the water-soluble polymer of spinning processing temperature (300 ℃), comprises polyoxyethylene (PEO) etc.; Described non-dissolubility pore-foaming agent is meant water-insoluble inorganic particulate, comprises that average grain diameter is the SiO of 0.01 ~ 5 μ m
2And CaCO
3Deng in the mixture of one or any ratio.With regard to the present invention in general, along with the increase of composite pore-forming, the porosity of gained hollow membrane and water flux are the trend of increase, but the corresponding decline of the mechanical strength of hollow membrane, and the solubility pore-foaming agent is particularly remarkable to the influence of the mechanical strength of film.Therefore for guaranteeing that the gained hollow membrane still keeps mechanical property preferably after removing water-soluble pore-foaming agent, in the described composite pore-forming, the mass percent that non-dissolubility pore-foaming agent accounts for composite pore-forming is 30 ~ 50% more excellent relatively, and the mass percent that composite pore-forming accounts for the system film system is 10 ~ 30% for excellent.
During prescription of the present invention was formed, described organic low molecular liquid required boiling point to be higher than spinning temperature, was the diluent of polymeric additive in the system film system.Organic low molecular liquid can be used as elasticizer plasticizing polymeric additive and composite pore-forming on the one hand, reduces the spinning temperature of system film system; It also serves as the lubricant of (per) fluoropolymer on the other hand, prevents that (per) fluoropolymer from producing burr in spinning process.Particularly, described organic low molecular liquid comprises dioctyl phthalate (DOP), the mixture of a kind of or arbitrary proportion in the dibutyl phthalate (DBP) etc.Experiment finds that along with the raising of organic low molecular content liquid, spinning temperature can correspondingly reduce, and the extraction back easily forms micropore, helps the raising of membrane flux.But too high organic low molecular content liquid can cause the hot strength of gained film and withstand voltage properties to reduce.So the more excellent addition scope of organic low molecular liquid is 5 ~ 20% of system film system gross mass among the present invention.
The present invention has designed the preparation method (abbreviation preparation method) of described (per) fluoropolymer doughnut perforated membrane simultaneously, this preparation method's technology is: earlier the film forming system is formed described polymeric additive, composite pore-forming and organic low molecular liquid and pour Forced Mixing in the mixing kettle into, form mixture of viscous form; Mix with the (per) fluoropolymer resin particle again; then the thing that is mixed is injected double screw extruder; under 300 ~ 360 ℃ of temperature; carry out the melt blending spinning through hollow-fiber module; the nascent film of preparation doughnut; wash through the water collection of conventional soln spinning at last and the after-drawing operation after, promptly obtain (per) fluoropolymer hollow-fibre membrane of the present invention.
The described spinning temperature scope of preparation method of the present invention is 300 ~ 360 ℃, and the temperature selection of concrete process implementing is relevant with the selection and the addition of polymeric additive and organic low molecular liquid.Preparation method of the present invention not only can effectively reduce spinning temperature, and energy savings makes the spinning process easy operating, and has enlarged the range of choice of pore-foaming agent, is convenient to industrializing implementation.
Among the preparation method of the present invention, further feature is that the system film system can be earlier through the dual-screw-stem machine granulation, and then carries out the melt blending spinning.Studies show that first granulation process can effectively improve the uniformity coefficient that polymeric additive and composite pore-forming are mixed with (per) fluoropolymer in the system film system, thus the uniformity of raising gained hollow fenestra.
Wash the uniformity of efficient and stretching for improving the water collection, the water collection among the preparation method of the present invention is washed with the after-drawing treatment process and is: nascent hollow-fibre membrane after the water-bath cooling, carries out after-drawing earlier through the spinneret draft operation again, carries out fixed length water collection at last and washes.Wherein, the drawing medium in the after-drawing technology is a water, i.e. after-drawing technology is that water-bath stretches, and the draft temperature scope is 40 ~ 80 ℃, preferentially selects 60 ~ 70 ℃, and draw ratio is 2 ~ 4 times.The temperature range that described water collection is washed technology is 50 ~ 90 ℃, preferentially selects 70 ~ 80 ℃.
The present invention does not address part and is applicable to prior art.
Provide specific embodiments of the invention below, but embodiment specifies the present invention, does not limit the protection domain of the present patent application claim.
Embodiment 1
With hexafluoropropene content is that 18% perfluoroethylene-propylene is the polymer substrate phase; With PVDF is polymeric additive; Composite pore-forming is the SiO of 0.01 μ m
2The mixture of powder and PEO, wherein the former is non-dissolubility pore-foaming agent, accounts for 30% of composite pore-forming total amount, the latter is the solubility pore-foaming agent, accounts for 70% of composite pore-forming total amount; Organic low molecular liquid selects DBP.Each set of dispense is such as following in the heterogeneous film forming system:
(per) fluoropolymer 40
Polymeric additive (PVDF) 10
Composite pore-forming 40
Organic low molecular liquid (DBP) 10,
Described PVDF, composite pore-forming and organic low molecular liquid are evenly obtained mixture of viscous form through the mixing kettle Forced Mixing, again with after granular (per) fluoropolymer resin mixes, the feeding double screw extruder, carry out the melt blending spinning membrane system through homemade doughnut spinning pack, twin-screw three district's temperature are respectively 290 ℃, 300 ℃, 310 ℃, the spinning head temperature is 320 ℃.After-drawing is selected 2 times, 3 times, 4 times, fully soaks after collection washes through 70 ℃ of water, promptly gets three kinds of described hollow membranes.Correspondence is designated as 1#, 2# and 3# film.
Embodiment 2
In embodiment 1, non-dissolubility pore-foaming agent SiO
2Proportioning be adjusted into 10% of pore-foaming agent total amount, the proportioning of solubility pore-foaming agent PEO is adjusted into 90%, other conditions are constant, obtain three kinds of described hollow membranes.Correspondence is designated as 4#, 5# and 6# film.
Embodiment 3
With hexafluoropropene content is that 18% perfluoroethylene-propylene is the polymer substrate phase; With PCTFE is polymeric additive; Composite pore-forming is 0.01 SiO
2The CaCO of powder, 5 μ m
3The mixture of powder and PEO, wherein the above two are non-dissolubility pore-foaming agent, and the two mass ratio is 1/1, accounts for 30% of composite pore-forming total amount, and the latter is the solubility pore-foaming agent, accounts for 70% of composite pore-forming total amount; Organic low molecular liquid selects DOP.Each set of dispense is such as following in the film forming system:
(per) fluoropolymer 60
Polymeric additive (PCTFE) 10
Composite pore-forming 20
Organic low molecular liquid (DOP) 10,
PCTFE, composite pore-forming and organic low molecular liquid are evenly obtained mixture of viscous form through the mixing kettle Forced Mixing, again with after granular (per) fluoropolymer resin mixes, the feeding double screw extruder, carry out the melt blending spinning membrane system through homemade doughnut spinning pack, twin-screw three district's temperature are respectively 300 ℃, 310 ℃, 320 ℃, the spinning head temperature is 330 ℃.After-drawing is selected 2 times, 3 times, 4 times, fully soaks after collection washes through 70 ℃ of water, promptly gets three kinds of hollow membranes of the present invention, and correspondence is designated as 7#, 8# and 9# film.
Embodiment 4
In embodiment 2, solubility pore-foaming agent PEO changes LiCl, the CaCl of 2 μ m respectively into
2, NaCl and KCl particle, draw ratio selects 3 times, other conditions are constant, make the hollow membrane of 4 kinds of prescriptions.Correspondence is designated as 10#, 11#, 12# and 13# film.
Embodiment 5
In embodiment 1, the mass percent of polymeric additive PVDF brings up to 20%, and composite pore-forming adjusts to 30%, and each set of dispense is such as following in the film forming system:
(per) fluoropolymer 40
Polymeric additive (PVDF) 20
Composite pore-forming 30
Organic low molecular liquid (DBP) 10,
Other conditions are constant, make described three kinds of hollow membranes, and correspondence is designated as 14#, 15# and 16# film.
Embodiment 6
In embodiment 3, organic low molecular liquid D OP mass percent is adjusted into 15%, and polymeric matrix (per) fluoropolymer mass percent is adjusted into 50%, and each set of dispense is such as following in the film forming system:
(per) fluoropolymer 50
Polymeric additive (PCTFE) 10
Composite pore-forming 20
Organic low molecular liquid (DOP) 20,
Other conditions are constant, make described three kinds of hollow membranes, and correspondence is designated as 17#, 18# and 19# film.
The present invention has carried out the test of water flux and fracture strength to embodiment 1-6 gained (per) fluoropolymer hollow membrane.Test result is listed in the table 1.Because the strong-hydrophobicity of (per) fluoropolymer, water flux is all tested after hollow membrane fully soaks alcohol immediately.The water flux test adopts formula (1) to calculate.
J=V/(A×t) （1）
(1) in the formula, J is a pure water flux, the L/ (m of unit
2H); V is a filtrate volume, the L of unit; A is the diffusion barrier effective area, the m of unit
2T is for obtaining V required time of volumes of filtrate, the h of unit.
The water flux and the fracture strength test tables of data of table 1 embodiment gained hollow membrane
| Sample number into spectrum | 1# | 2# | 3# | 4# | 5# | 6# | 7# | 8# |
| Water flux (L/m 2·h） | 134.6 | 213.5 | 451.8 | 183.02 | 269.73 | 514.50 | 57. 2 | 90.4 |
| Fracture strength (Mpa) | 35.8 | 26.4 | 18.3 | 22.3 | 16.4 | 13.1 | 45.1 | 33.6 |
| Sample number into spectrum | 9# | 10# | 11# | 12# | 13# | 14# | 15# | 16# |
| Water flux (L/m 2·h） | 105.5 | 246.5 | 252.9 | 265. 2 | 253.1 | 94.03 | 178.46 | 330.3 |
| Fracture strength (Mpa) | 24.9 | 17.8 | 16.2 | 18.3 | 15.4 | 27.4 | 22.4 | 20.1 |
| Sample number into spectrum | 17# | 18# | 19# | ? | ? | ? | ? | ? |
| Water flux (L/m 2·h） | 85.1 | 124.3 | 242.9 | ? | ? | ? | ? | ? |
| Fracture strength (Mpa) | 23.9 | 18.8 | 14.2 | ? | ? | ? | ? | ? |
Claims (5)
1. (per) fluoropolymer doughnut perforated membrane, the film forming system percentage by weight prescription of this film consists of:
(per) fluoropolymer 40 ~ 60;
Polymeric additive 10 ~ 30;
Composite pore-forming 10 ~ 30;
Organic low molecular liquid 5 ~ 20, each component sum is 100%,
Wherein, described (per) fluoropolymer is tetrafluoroethene base and the perfluor second monomer copolymerization modified product, comprise perfluoroethylene-propylene, tetrafluoroethene-perfluoro propyl vinyl ether, or the blend of perfluoroethylene-propylene and tetrafluoroethene-perfluoro propyl vinyl ether arbitrary proportion, described perfluor second monomer is hexafluoropropene, perfluoroalkyl vinyl ether or ethene; Described polymeric additive is the mixture of fluorine-containing alkane polymer or fluorine-containing alkane polymer, comprises Kynoar or polytrifluorochloroethylene; Described composite pore-forming comprises solubility pore-foaming agent and non-dissolubility pore-foaming agent, and the solubility pore-foaming agent is meant water-soluble substances, comprises the mixture of water-soluble inorganic particle, water-soluble polymer or water-soluble inorganic particle and water-soluble polymer arbitrary proportion; Described water-soluble inorganic particle comprises LiCl, the CaCl of average grain diameter 0.01-5 μ m
2, among NaCl and the KCl any one; Described water-soluble polymer is meant that decomposition temperature is higher than the water-soluble polymer of its spinning processing temperature, comprises polyoxyethylene; Described non-dissolubility pore-foaming agent is meant water-insoluble inorganic particulate, comprises that average grain diameter is the SiO of 0.01-5 μ m
2Or CaCO
3In a kind of, perhaps SiO
2And CaCO
3The mixture of arbitrary proportion; Described organic low molecular liquid is the diluent of high boiling polymeric additive, comprises a kind of in dioctyl phthalate or the dibutyl phthalate or the mixture of dioctyl phthalate and dibutyl phthalate arbitrary proportion.
2. the preparation method of the described (per) fluoropolymer doughnut of claim 1 perforated membrane, the technology that this preparation method adopts is: earlier the film forming system formulation is formed described polymeric additive, composite pore-forming and organic low molecular liquid and pour Forced Mixing in the mixing kettle into, form mixture of viscous form; Again mixture and (per) fluoropolymer resin particle are mixed; Then the thing that is mixed is injected double screw extruder, under 300-360 ℃ of temperature, carry out the melt blending spinning through hollow-fiber module, the nascent film of preparation doughnut, wash through the water collection of conventional soln spinning at last and the after-drawing operation after, promptly obtain (per) fluoropolymer hollow-fibre membrane of the present invention.
3. according to the preparation method of the described (per) fluoropolymer doughnut of claim 2 perforated membrane, it is characterized in that described film forming system earlier through the dual-screw-stem machine granulation, and then carry out the melt blending spinning.
4. according to the preparation method of claim 2 or 3 described (per) fluoropolymer doughnut perforated membranes, it is characterized in that described water collection is washed with after-drawing technology is: nascent hollow-fibre membrane is earlier through the spinneret draft operation, after the water-bath cooling, carry out after-drawing again, carry out fixed length water collection at last and wash; Wherein, to wash the temperature range of technology be 50 ~ 90 ℃ for water collection; Drawing medium in the after-drawing technology is a water, and the draft temperature scope is 40 ~ 80 ℃, and draw ratio is 2 ~ 4 times.
5. according to the preparation method of the described (per) fluoropolymer doughnut of claim 4 perforated membrane, it is characterized in that the temperature range that described water collection is washed technology is 70 ~ 80 ℃; The draft temperature scope is 60 ~ 70 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340732A2 (en) * | 1988-05-04 | 1989-11-08 | Millipore Corporation | Fluorocarbon membranes and process for making fluorocarbon membranes |
| CN1642628A (en) * | 2002-03-19 | 2005-07-20 | 密科理股份有限公司 | Hollow fiber membrane contact apparatus and process |
| EP1154842B1 (en) * | 1999-01-29 | 2006-07-12 | Entegris, Inc. | Skinned hollow fiber membrane and method of manufacture |
| CN101053778A (en) * | 2007-05-16 | 2007-10-17 | 天津工业大学 | Method for making poly-meta-fluoethylene hollow fibre porous membrane and products thereof |
| CN101322922A (en) * | 2008-07-21 | 2008-12-17 | 天津工业大学 | Hollow fiber film and method for producing the same |
-
2010
- 2010-08-18 CN CN2010102559498A patent/CN101884878B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0340732A2 (en) * | 1988-05-04 | 1989-11-08 | Millipore Corporation | Fluorocarbon membranes and process for making fluorocarbon membranes |
| EP1154842B1 (en) * | 1999-01-29 | 2006-07-12 | Entegris, Inc. | Skinned hollow fiber membrane and method of manufacture |
| CN1642628A (en) * | 2002-03-19 | 2005-07-20 | 密科理股份有限公司 | Hollow fiber membrane contact apparatus and process |
| CN101053778A (en) * | 2007-05-16 | 2007-10-17 | 天津工业大学 | Method for making poly-meta-fluoethylene hollow fibre porous membrane and products thereof |
| CN101322922A (en) * | 2008-07-21 | 2008-12-17 | 天津工业大学 | Hollow fiber film and method for producing the same |
Non-Patent Citations (1)
| Title |
|---|
| 《有机氟工业》 20091231 徐洪，杨永祥 聚全氟乙丙烯(FEP)性能与成型方法和应用 31-35 1-5 , 第3期 2 * |
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