CN109078509A - A kind of perfluoroethylene-propylene hollow-fibre membrane and preparation method thereof - Google Patents
A kind of perfluoroethylene-propylene hollow-fibre membrane and preparation method thereof Download PDFInfo
- Publication number
- CN109078509A CN109078509A CN201710447581.7A CN201710447581A CN109078509A CN 109078509 A CN109078509 A CN 109078509A CN 201710447581 A CN201710447581 A CN 201710447581A CN 109078509 A CN109078509 A CN 109078509A
- Authority
- CN
- China
- Prior art keywords
- perfluoroethylene
- propylene
- hollow
- doughnut
- fibre membrane
- 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
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The present invention provides a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane comprising: a) by perfluoroethylene-propylene, pore-foaming agent and dispersant, perfluoroethylene-propylene doughnut is made；B) the perfluoroethylene-propylene doughnut is placed in closed container, and the temperature of closed container is risen to 270 DEG C~360 DEG C；C) it is passed through supercritical carbon dioxide to pressure into closed container and reaches 25MPa~40MPa；D) to the closed container carry out release, make supercritical carbon dioxide foaming, obtain include multiple first apertures perfluoroethylene-propylene doughnut primary membrane；E) the perfluoroethylene-propylene doughnut primary membrane is soaked in etching solution, so that pore-foaming agent is etched and forms multiple second apertures, obtain perfluoroethylene-propylene hollow-fibre membrane.The present invention also provides a kind of perfluoroethylene-propylene hollow-fibre membranes.
Description
Technical field
The present invention relates to polymeric film material technical field more particularly to a kind of perfluoroethylene-propylene hollow-fibre membrane and its
Preparation method.
Background technique
Hollow-fibre membrane is a kind of shape in threadiness, the film with self-supporting effect.Currently, common hollow-fibre membrane
Material is Kynoar (PVDF), polysulfones (PS), polyether sulfone (POS), sulfonated polysulfone (SPS), polyacrylonitrile (PAN) and fiber
Element etc. commonly uses non-solvent precipitation gel phase inversion (NIPS) preparation.But hollow-fibre membrane intensity difference prepared by NIPS method,
Film wire easy fracture in use process.Also the hollow-fibre membrane for thering is researcher to enhance by the preparation of supporting layer method, but resin and branch
Support layer bond properties it is poor, be easy to produce in preparation process burr, film layer coating it is unequal bad.
Perfluoroethylene-propylene (copolymer) (FEP) has chemical stability outstanding, good corrosion resistance and excellent high temperature performance,
Just gradually by the concern of researcher.For example Xiao Changfa et al. is used and the extrusion moldings such as organic solvent and pore-foaming agent is added, then
It is washed by extraction and is prepared for (per) fluoropolymer hollow-fibre membrane with stretching device stretching.But with largely having in the preparation method
Solvent keeps feeding in extrusion process difficult, and organic solvent is volatile when high temperature, has biggish security risk and environment hidden
Suffer from.Therefore, environmentally protective FEP doughnut membrane preparation method is developed to have great importance.
Summary of the invention
In view of the above-mentioned problems, the purpose of the present invention is to provide a kind of environmentally protective perfluoroethylene-propylene hollow-fibre membranes
And preparation method thereof.
The present invention provides a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane comprising following steps:
A) by perfluoroethylene-propylene, pore-foaming agent and dispersant, and perfluoroethylene-propylene doughnut is made；
B) the perfluoroethylene-propylene doughnut is placed in closed container, and the temperature of closed container is risen to 270
DEG C~360 DEG C；
C) pressure for being passed through supercritical carbon dioxide to closed container into closed container reaches 25MPa~40MPa, and
Predetermined time T is kept under the pressure, is uniformly distributed in supercritical carbon dioxide in perfluoroethylene-propylene doughnut；
D) release is carried out to the closed container, makes the supercritical carbon dioxide in the perfluoroethylene-propylene doughnut
Foaming, obtain perfluoroethylene-propylene doughnut primary membrane, wherein the release speed of the closed container be more than or equal to
10MPa/s, the perfluoroethylene-propylene doughnut primary membrane include multiple first apertures；
E) the perfluoroethylene-propylene doughnut primary membrane is soaked in an etching solution, makes the perfluoroethylene third
Pore-foaming agent in alkene doughnut primary membrane is etched and forms multiple second apertures, obtains perfluoroethylene-propylene doughnut
Film.
The present invention also provides a kind of perfluoroethylene-propylene hollow-fibre membrane that above-mentioned preparation method obtains, the perfluoroethylenes
Propylene hollow-fibre membrane includes multiple apertures, and the pore size of the aperture on the surface of the perfluoroethylene-propylene hollow-fibre membrane is
1 nanometer~1 micron, the pore size of the aperture of the inside of the perfluoroethylene-propylene hollow-fibre membrane is 1 nanometer~100 micro-
Rice, the density of the perfluoroethylene-propylene hollow-fibre membrane are 0.5~1.5g/cm3。
Compared to the prior art, this preparation method carries out secondary aperture by two different aperture mechanism, is formed poly- complete
Fluoro ethyl propene hollow-fibre membrane.Specifically, uniformly mix perfluoroethylene-propylene with pore-foaming agent, dispersing agent in step a), so that
The pore-foaming agent, dispersing agent are uniformly distributed in premix.In in step c) and d), by the way that the temperature of closed container is risen to
270 DEG C~360 DEG C, so that perfluoroethylene-propylene becomes soft phase at high temperature.After being passed through supercritical carbon dioxide, overcritical two
Carbonoxide is sufficiently dissolved and is spread in the perfluoroethylene-propylene of soft phase.10MPa/ (is more than or equal to higher release speed again
S) release, carbon dioxide expanded, the escape of above-critical state are carried out to the closed container, gas can break through perfluoroethylene in steep that wall
The soft phase of propylene and form multiple first apertures.It is appreciated that pore-foaming agent can be exposed by multiple first aperture part.
In step f), when the perfluoroethylene-propylene doughnut primary membrane is soaked in the etching solution, the poly- perfluor
The pore-foaming agent and the etching solution of the nascent film surface of second propylene doughnut act on, and in the hollow fibre of the perfluoroethylene-propylene
The surface for tieing up primary membrane forms the second aperture, and the etching solution is slowly via at the beginning of the perfluoroethylene-propylene doughnut at this time
Second aperture on the surface of filming reaches the first aperture inside the perfluoroethylene-propylene doughnut primary membrane, and will pass through
The pore-foaming agent etching of first aperture exposure, and multiple the second fine apertures are further formed in the inner wall of the first aperture.Finally
The perfluoroethylene-propylene hollow-fibre membrane include multiple apertures (general designation of the first aperture and the second aperture).That is, the preparation
In method, the second aperture is formed on the basis of the first aperture, the hollow fibre of the secondary obtained perfluoroethylene-propylene of aperture
Tieing up film has high opening rate.It is the preparation method simple process of the perfluoroethylene-propylene hollow-fibre membrane, high-efficient, it is at low cost, green
Colour circle is protected, and industrialized production is suitble to.
The perfluoroethylene-propylene hollow-fibre membrane has high opening rate, and the pore size of the aperture is moderate (at 100 microns
Below), aperture is evenly distributed.The perfluoroethylene-propylene hollow-fibre membrane mechanical strength is good, corrosion resistance and thermal stability are excellent
It is good, it can be used as seperation film and be applied to the fields such as water process, environmental protection, chemical industry, the energy, medicine, food, biology.
Detailed description of the invention
Fig. 1 and Fig. 2 is the profile scanning Electronic Speculum for the perfluoroethylene-propylene hollow-fibre membrane that the embodiment of the present invention 1 obtains
(SEM) photo；
Fig. 3 is the surface SEM photograph for the perfluoroethylene-propylene hollow-fibre membrane that the embodiment of the present invention 1 obtains.
Fig. 4 and Fig. 5 is the section SEM photograph for the perfluoroethylene-propylene hollow-fibre membrane that the embodiment of the present invention 2 obtains.
Specific embodiment
Below in conjunction with the attached drawing in embodiment of the present invention, the technical solution in embodiment of the present invention is carried out clear
Chu is fully described by, it is clear that described embodiment is only some embodiments of the invention, rather than whole realities
Apply mode.Based on the embodiment in the present invention, those of ordinary skill in the art institute without creative efforts
The every other embodiment obtained, shall fall within the protection scope of the present invention.
The present invention provides a kind of preparation methods of perfluoroethylene-propylene hollow-fibre membrane comprising following steps:
A) by perfluoroethylene-propylene, pore-foaming agent and dispersant, and perfluoroethylene-propylene doughnut is made；
B) the perfluoroethylene-propylene doughnut is placed in closed container, and the temperature of closed container is risen to 270
DEG C~360 DEG C；
C) pressure for being passed through supercritical carbon dioxide to closed container into closed container reaches 25MPa~40MPa, and
Predetermined time T is kept under the pressure, is uniformly distributed in supercritical carbon dioxide in perfluoroethylene-propylene doughnut；
D) release is carried out to the closed container, makes the supercritical carbon dioxide in the perfluoroethylene-propylene doughnut
Foaming, obtain perfluoroethylene-propylene doughnut primary membrane, wherein the release speed of the closed container be more than or equal to
10MPa/s, the perfluoroethylene-propylene doughnut primary membrane include multiple first apertures；
E) the perfluoroethylene-propylene doughnut primary membrane is soaked in an etching solution, makes the perfluoroethylene third
Pore-foaming agent in alkene doughnut primary membrane is etched and forms multiple second apertures, obtains perfluoroethylene-propylene doughnut
Film.
In step a), perfluoroethylene-propylene and pore-foaming agent and dispersing agent can be passed through into twin-screw, single screw rod or plunger type
The mode of Screw Extrusion squeezes out obtained perfluoroethylene-propylene doughnut.
The pore-foaming agent includes inorganic carbonate and/or water-soluble polymer.Wherein the inorganic carbonate be calcium carbonate,
At least one of magnesium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate, barium carbonate.The water-soluble polymer is polyoxyethylene.
The mass percent that the pore-foaming agent accounts for the premix is 1%~10%.
The effect of the dispersing agent is to reduce the melt viscosity of perfluoroethylene-propylene, improves its melt strength, makes subsequent
Supercritical carbon dioxide can sufficiently be dissolved and is spread in perfluoroethylene-propylene.The dispersing agent is stearic amide, stearic acid
At least one of salt, oleamide, erucyl amide, ethylene bis stearamide, the quality of the dispersing agent are the premix
The 0.1%~1% of quality.The dispersing agent can volatilize in subsequent step d) release, can also be dissolved in step e) certainly
In etching solution, to be removed.
In step b), by being increased to the temperature in closed container, it can make at perfluoroethylene-propylene doughnut
In a kind of special soft phase state, which is not complete fluid, and the perfluoroethylene-propylene doughnut is still
Doughnut state can be so kept, to be conducive to the supercritical carbon dioxide " dissolution " of step c in the hollow fibre of perfluoroethylene-propylene
In dimension, and it is evenly distributed.It is understood that being somebody's turn to do " dissolution " is not for real meaning salt is soluble in water general molten
Solution, but a kind of special dissolved state.Exactly because the temperature of the closed container increases, perfluoroethylene-propylene doughnut
In soft phase, therefore, by supercritical carbon dioxide uniform dissolution and can expand in shorter predetermined time T (being more than or equal to 8 minutes)
It dissipates in perfluoroethylene-propylene doughnut；The time is greatly saved in this, improves preparation efficiency.
Temperature in the closed container can be set according to the specific type of the perfluoroethylene-propylene, as long as making poly- complete
Fluoro ethyl propene is in soft phase.For 270 DEG C of lower limit temperature in the closed container, higher than the glass of perfluoroethylene-propylene
Change transition temperature, makes perfluoroethylene-propylene in soft phase；It is described for 360 DEG C of ceiling temperature in the closed container
The ceiling temperature of closed container cannot cause perfluoroethylene-propylene to melt completely.
The closed container can be autoclave.It further include one to closed container before increasing the temperature of closed container
It is inside passed through carbon dioxide, excludes the air in closed container.
In step c), the pressure that can be passed through supercritical carbon dioxide to closed container into closed container reaches 25MPa
~40MPa, at this point, can be obtained via the foaming process of step d), pore size is consistent and pore size is the more of micron level
A first aperture.
In step d), when carrying out release to the closed container with higher release speed (be more than or equal to 10MPa/s),
Carbon dioxide expanded, the escape of above-critical state, gas can break through the soft phase of perfluoroethylene-propylene in steep that wall and form multiple first and hold
Hole.It is appreciated that pore-foaming agent can be exposed by multiple first aperture part.
Preferably, the release speed of the closed container is more than or equal to 15MPa/s, at this point, aperture can be obtained after foaming
Size is more consistent and pore size is multiple first apertures of micron level.
In step e), when the perfluoroethylene-propylene doughnut primary membrane is soaked in the etching solution,
The pore-foaming agent and the etching solution of the nascent film surface of the perfluoroethylene-propylene doughnut act on, and in the perfluoroethylene
The surface of propylene doughnut primary membrane forms the second aperture, and the etching solution is slowly via the perfluoroethylene-propylene at this time
What second aperture on the surface of doughnut primary membrane reached inside the perfluoroethylene-propylene doughnut primary membrane first opens
Hole, and multiple fine the will be further formed in the inner wall of the first aperture by the pore-foaming agent etching of the first aperture exposure
Two apertures.The final perfluoroethylene-propylene hollow-fibre membrane includes multiple apertures (system of the first aperture and the second aperture
Claim).That is, the second aperture is formed on the basis of the first aperture in the preparation method, the secondary obtained poly- perfluor of aperture
Second propylene hollow-fibre membrane has high opening rate.The pore size of the aperture is moderate (at 100 microns or less).
The etching solution is acid solution or water.The acid solution be sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid,
At least one of citric acid.When the pore-foaming agent is inorganic carbonate, the etching solution selects acid solution, utilizes nothing
Reacting between machine carbonate and the acid solution and be dissolved inorganic carbonate and " chemically etch " is fallen, form second
Aperture.When the pore-foaming agent is water-soluble polymer polyoxyethylene, the etching solution is water or acid solution, benefit
Water is dissolvable in water and " physical etching " is fallen with polyoxyethylene, forms the second aperture.
Mole solubility of the acid solution is unlimited, preferably 1.5mol/L~4.0mol/L.The perfluoroethylene-propylene
It is 1 hour~72 hours that doughnut primary membrane, which immerses the soaking time in the etching solution, and preferably 1 hour~24 is small
When.The soaking process can carry out at room temperature.
Further, before the perfluoroethylene-propylene doughnut primary membrane is soaked in an etching solution, into one
Step includes the steps that a pair of perfluoroethylene-propylene doughnut primary membrane is stretched.Drawing medium is water, draft temperature
Range is 40 DEG C~80 DEG C, and draw ratio is 1.5 times~5 times.
Further, the perfluoroethylene-propylene doughnut primary membrane can also carry out a water after etching solution immersion
The step of extraction is washed, to remove the impurity such as the remaining etching solution in the perfluoroethylene-propylene doughnut primary membrane.Water extraction
The temperature range for washing technique is 20 DEG C~90 DEG C, and the time is 0.5 hour~48 hours.
It also needs to be intended that herein, the aperture of the aperture on the surface of the perfluoroethylene-propylene hollow-fibre membrane finally obtained is small
The aperture of the aperture in portion in the inner.The perfluoroethylene-propylene doughnut primary membrane that step e) is obtained is similar in life
After steamed bun evaporation, internal aperture is big, and surface is substantially without hole, and the application step f) etching is exactly in perfluoroethylene-propylene
The surface of hollow fiber primary membrane performs etching to form lesser aperture, and further shape on the basis of the first aperture inside it
Aperture at the second aperture, i.e. internal aperture is big.
The present invention also provides a kind of perfluoroethylene-propylene hollow-fibre membranes obtained using above-mentioned preparation method.It is described poly- complete
Fluoro ethyl propene hollow-fibre membrane includes multiple apertures.The aperture is the general designation of above-mentioned first aperture and the second aperture.It is the multiple
It is interconnected between aperture.The hole wall of the aperture is relatively thin.
FIG. 1 to FIG. 2 is please referred to, the section of perfluoroethylene-propylene hollow-fibre membrane is equally distributed spongy abscess,
Inside and outside epidermis is thin.The pore size of the aperture on the surface of the perfluoroethylene-propylene hollow-fibre membrane is 1 nanometer~1 micron,
The pore size of the aperture of the inside of the perfluoroethylene-propylene hollow-fibre membrane is 1 nanometer~100 microns, the perfluoroethylene
The density of propylene hollow-fibre membrane is 0.5~1.5g/cm3。
The perfluoroethylene-propylene hollow-fibre membrane has high opening rate, and mechanical strength is good, corrosion resistance and heat are steady
It is qualitative excellent, it can be used as seperation film and be applied to the fields such as water process, environmental protection, chemical industry, the energy, medicine, food, biology.
It is the preparation method simple process of the perfluoroethylene-propylene hollow-fibre membrane, high-efficient, it is at low cost, environmentally protective, it fits
Close industrialized production.
The preparation method of perfluoroethylene-propylene hollow-fibre membrane of the invention is illustrated combined with specific embodiments below:
Embodiment 1
945g perfluoroethylene-propylene (FEP), 50g calcium carbonate, 5g stearic amide are uniformly mixed by step (1), by double
FEP doughnut is made in screw extruder melting extrusion, and extrusion temperature is 300~330 DEG C.
Obtained FEP doughnut is placed in the autoclave of connection supercritical carbon dioxide device by step (2), is passed through two
Carbonoxide, low pressure purge 4 minutes.Autoclave temp is set as 315 DEG C.
Step (3) is passed through supercritical carbon dioxide fluid pressure into kettle and reaches 30MPa after temperature reaches；Constant temperature is permanent
Pressure is kept for 20 minutes.
Step (4) opens autoclave pressure-relief valve, is unloaded with the speed of 15MPa/s and is depressed into normal pressure, and it is nascent to obtain FEP doughnut
Film.
Resulting FEP doughnut primary membrane is immersed in the dilute hydrochloric acid solution that mass percent is 2% by step (5)
48h；It is then placed in deionized water and embathes for 24 hours, temperature is 60 DEG C, and shakes processing, obtains FEP hollow-fibre membrane.
Referring to Figure 1 and Fig. 2, the section of the FEP hollow-fibre membrane are uniformly distributed multiple micropores.After tested, the hollow fibre of FEP
The average pore size for tieing up the micropore of the section of film is 13.9 μm, and inside and outside cortex average thickness is respectively 2.6 μm and 1.7 μm.
Fig. 3 is referred to, which is distributed with multiple micropores.
Embodiment 2
The preparation method of the FEP hollow-fibre membrane of the embodiment is substantially the same manner as Example 1, the difference is that, in step
Suddenly before FEP doughnut primary membrane is soaked in dilute hydrochloric acid by (5), FEP doughnut primary membrane is subjected to stretch processing, wherein
Stretching ratio is 2 times, and drawing medium is water, and draft temperature is 70 DEG C.
See Fig. 4, Fig. 5, the average pore size of the micropore of the section of gained FEP hollow-fibre membrane is 11.3 μm, inside and outside cortex
Average thickness is respectively 1.9 μm and 1.1 μm.
The above is a preferred embodiment of the present invention, it is noted that for those skilled in the art
For, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also considered as
Protection scope of the present invention.
Claims (8)
1. a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane comprising following steps:
A) by perfluoroethylene-propylene, pore-foaming agent and dispersant, and perfluoroethylene-propylene doughnut is made；
B) the perfluoroethylene-propylene doughnut is placed in closed container, and by the temperature of closed container rise to 270 DEG C~
360℃；
C) pressure for being passed through supercritical carbon dioxide to closed container into closed container reaches 25MPa~40MPa, and in the pressure
Predetermined time T is kept under power, is uniformly distributed in supercritical carbon dioxide in perfluoroethylene-propylene doughnut；
D) release is carried out to the closed container, sends out the supercritical carbon dioxide in the perfluoroethylene-propylene doughnut
Bubble, obtains perfluoroethylene-propylene doughnut primary membrane, wherein the release speed of the closed container is more than or equal to 10MPa/
S, the perfluoroethylene-propylene doughnut primary membrane include multiple first apertures；
E) the perfluoroethylene-propylene doughnut primary membrane is soaked in an etching solution, is made in the perfluoroethylene-propylene
Pore-foaming agent in hollow fiber primary membrane is etched and forms multiple second apertures, obtains perfluoroethylene-propylene hollow-fibre membrane.
2. a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane as described in claim 1, which is characterized in that step a)
Described in dispersing agent be stearic amide, stearate, oleamide, erucyl amide, ethylene bis stearamide at least one,
The dispersing agent accounts for the 0.1%~1% of the quality of the premix.
3. a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane as described in claim 1, which is characterized in that step a)
Described in pore-foaming agent include inorganic carbonate and/or water-soluble polymer, wherein the inorganic carbonate is calcium carbonate, carbonic acid
At least one of magnesium, sodium bicarbonate, sodium carbonate, potassium carbonate, barium carbonate, the water-soluble polymer are polyoxyethylene.
4. a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane as described in claim 1, which is characterized in that step a)
Described in pore-foaming agent account for the premix mass percent be 1%~10%.
5. a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane as described in claim 1, which is characterized in that step c)
Described in predetermined time T be more than or equal to 10 minutes.
6. a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane as described in claim 1, which is characterized in that step e)
Described in etching solution be acid solution or water, the acid solution be sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid, citric acid
At least one of.
7. a kind of preparation method of perfluoroethylene-propylene hollow-fibre membrane as described in claim 1, which is characterized in that in step
It e) further comprise described in a pair in front of the perfluoroethylene-propylene doughnut primary membrane is soaked in an etching solution
The step of perfluoroethylene-propylene doughnut primary membrane is stretched.
8. a kind of using the perfluoroethylene-propylene hollow-fibre membrane obtained such as any one of claim 1 to 7 preparation method, feature
It is, the perfluoroethylene-propylene hollow-fibre membrane includes multiple apertures, the surface of the perfluoroethylene-propylene hollow-fibre membrane
Aperture pore size be 1 nanometer~1 micron, the aperture of the aperture of the inside of the perfluoroethylene-propylene hollow-fibre membrane is big
Small is 1 nanometer~100 microns, and the density of the perfluoroethylene-propylene hollow-fibre membrane is 0.5~1.5g/cm3。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710447581.7A CN109078509B (en) | 2017-06-14 | 2017-06-14 | Fluorinated ethylene propylene hollow fiber membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710447581.7A CN109078509B (en) | 2017-06-14 | 2017-06-14 | Fluorinated ethylene propylene hollow fiber membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109078509A true CN109078509A (en) | 2018-12-25 |
| CN109078509B CN109078509B (en) | 2020-10-23 |
Family
ID=64839407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710447581.7A Expired - Fee Related CN109078509B (en) | 2017-06-14 | 2017-06-14 | Fluorinated ethylene propylene hollow fiber membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109078509B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110898681A (en) * | 2019-09-26 | 2020-03-24 | 上海稀点新材料科技有限公司 | Flat membrane with nano porous structure and preparation method thereof |
| CN112030254A (en) * | 2020-08-28 | 2020-12-04 | 平湖爱之馨环保科技有限公司 | Microporous fiber and manufacturing method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613548A (en) * | 2004-09-24 | 2005-05-11 | 浙江大学 | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology |
| CN101580600A (en) * | 2009-06-18 | 2009-11-18 | 上海交通大学 | Method for preparing perfluoroethylene-propylene microcellular foam material |
| CN102702692A (en) * | 2012-05-23 | 2012-10-03 | 常熟市阳光针织布业有限公司 | Antimicrobial porous polyester chip and method for preparing and processing POY filament yarns and DTY yarns |
| CN103467894A (en) * | 2013-08-23 | 2013-12-25 | 中国科学院宁波材料技术与工程研究所 | Polyvinylidene fluoride/graphene composite material and preparation method thereof |
| CN105001512A (en) * | 2015-07-01 | 2015-10-28 | 中国科学院宁波材料技术与工程研究所 | Open-cell polymer foam material and preparation method therefor |
-
2017
- 2017-06-14 CN CN201710447581.7A patent/CN109078509B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1613548A (en) * | 2004-09-24 | 2005-05-11 | 浙江大学 | Method for preparing polymer microporous membrane by supercritical or nearcritical CO2 technology |
| CN101580600A (en) * | 2009-06-18 | 2009-11-18 | 上海交通大学 | Method for preparing perfluoroethylene-propylene microcellular foam material |
| CN102702692A (en) * | 2012-05-23 | 2012-10-03 | 常熟市阳光针织布业有限公司 | Antimicrobial porous polyester chip and method for preparing and processing POY filament yarns and DTY yarns |
| CN103467894A (en) * | 2013-08-23 | 2013-12-25 | 中国科学院宁波材料技术与工程研究所 | Polyvinylidene fluoride/graphene composite material and preparation method thereof |
| CN105001512A (en) * | 2015-07-01 | 2015-10-28 | 中国科学院宁波材料技术与工程研究所 | Open-cell polymer foam material and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| LARISSA ZIRKEL等: "Foaming of thin films of a fluorinated ethylene propylene copolymer using supercritical carbon dioxide", 《THE JOURNAL OF SUPERCRITICAL FLUIDS》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110898681A (en) * | 2019-09-26 | 2020-03-24 | 上海稀点新材料科技有限公司 | Flat membrane with nano porous structure and preparation method thereof |
| CN110898689A (en) * | 2019-09-26 | 2020-03-24 | 上海稀点新材料科技有限公司 | Flat membrane with nano porous structure and preparation method thereof |
| CN110898688A (en) * | 2019-09-26 | 2020-03-24 | 上海稀点新材料科技有限公司 | Inorganic flat membrane with nano porous structure and preparation method thereof |
| CN110898688B (en) * | 2019-09-26 | 2021-10-01 | 上海稀点新材料科技有限公司 | Inorganic flat membrane with nano porous structure and preparation method thereof |
| CN110898689B (en) * | 2019-09-26 | 2021-11-16 | 上海稀点新材料科技有限公司 | Flat membrane with nano porous structure and preparation method thereof |
| CN110898681B (en) * | 2019-09-26 | 2021-11-16 | 上海稀点新材料科技有限公司 | Flat membrane with nano porous structure and preparation method thereof |
| CN112030254A (en) * | 2020-08-28 | 2020-12-04 | 平湖爱之馨环保科技有限公司 | Microporous fiber and manufacturing method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109078509B (en) | 2020-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112538162B (en) | Modified aramid polymer, aramid film casting solution, lithium battery diaphragm, preparation method and lithium battery | |
| WO2006001528A1 (en) | Porous membrane for water treatment and process for producing the same | |
| AU2015235572B2 (en) | Hollow fiber membrane, and method for producing hollow fiber membrane | |
| JP5154784B2 (en) | filter | |
| CN105126648A (en) | Method for preparing meshed PVDF (polyvinylidene fluoride) film based on PVA (polyvinyl alcohol) gel | |
| JP2012525966A (en) | Fluorine-based hollow fiber membrane and method for producing the same | |
| CN109078509A (en) | A kind of perfluoroethylene-propylene hollow-fibre membrane and preparation method thereof | |
| JPWO2014054346A1 (en) | Composite separation membrane | |
| JPS61293830A (en) | Manufacture of polytetrafluoroethylene porous film | |
| CN110878133A (en) | Hydrophilic polytetrafluoroethylene microporous membrane and preparation method thereof | |
| JP2628788B2 (en) | Method for producing microporous membrane and fusing resistant microporous membrane produced by the method | |
| CA3078177A1 (en) | Method for producing polyphenylsulfone hollow fiber membrane for humidifying membranes | |
| KR20120059755A (en) | Method for manufacturing a hollow fiber membrane for water treatment using cellulose resin | |
| JP4781691B2 (en) | Porous membrane and method for producing the same | |
| CN108568216B (en) | Polylactic acid microporous membrane and manufacturing method thereof | |
| JP2002348401A (en) | Polyketone porous material | |
| JPH07119303B2 (en) | Method for producing tetrafluoroethylene resin porous membrane | |
| CN109078500A (en) | A kind of fluoropolymer plate membrane and preparation method thereof | |
| CN115121133A (en) | PVDF film for water treatment and preparation method thereof | |
| TW201927885A (en) | Porous fluorine resin film, preparation method thereof and automotive vent filter | |
| KR20160026820A (en) | Porous polytetrafluoroethylene film and method for producing same | |
| JPH1135716A (en) | Production of porous polytetrafluoroethylene film | |
| CN110882634A (en) | Formula of ethylene-chlorotrifluoroethylene copolymer microporous membrane and method for preparing microporous membrane by using formula | |
| EP2671629A1 (en) | Membrane-forming dope for carbon membranes and process for producing carbon hollow fiber membrane using same | |
| KR20190060552A (en) | Composition for hollow fiber membrane, method for preparing hollow fiber membrane using the same, and hollow fiber membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201023 Termination date: 20210614 |