CN109078509B - Fluorinated ethylene propylene hollow fiber membrane and preparation method thereof - Google Patents
Fluorinated ethylene propylene hollow fiber membrane and preparation method thereof Download PDFInfo
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- CN109078509B CN109078509B CN201710447581.7A CN201710447581A CN109078509B CN 109078509 B CN109078509 B CN 109078509B CN 201710447581 A CN201710447581 A CN 201710447581A CN 109078509 B CN109078509 B CN 109078509B
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- 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
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- 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
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- 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
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention provides a preparation method of a fluorinated ethylene propylene hollow fiber membrane, which comprises the following steps: a) mixing the fluorinated ethylene propylene, a pore-forming agent and a dispersing agent to prepare the fluorinated ethylene propylene hollow fiber; b) placing the fluorinated ethylene propylene hollow fiber in a closed container, and raising the temperature of the closed container to 270-360 ℃; c) introducing supercritical carbon dioxide into the closed container until the pressure reaches 25-40 MPa; d) releasing the pressure of the closed container to foam the supercritical carbon dioxide to obtain a fluorinated ethylene propylene hollow fiber primary membrane comprising a plurality of first openings; e) and soaking the perfluorinated ethylene propylene copolymer hollow fiber primary membrane in an etching solution to etch the pore-forming agent to form a plurality of second openings, thus obtaining the perfluorinated ethylene propylene copolymer hollow fiber membrane. The invention also provides a perfluorinated ethylene propylene copolymer hollow fiber membrane.
Description
Technical Field
The invention relates to the technical field of polymer membrane materials, in particular to a fluorinated ethylene propylene hollow fiber membrane and a preparation method thereof.
Background
The hollow fiber membrane is a membrane which is in a fiber shape and has a self-supporting function. At present, the materials of the commonly used hollow fiber membrane are polyvinylidene fluoride (PVDF), Polysulfone (PS), Polyethersulfone (POS), Sulfonated Polysulfone (SPS), Polyacrylonitrile (PAN), cellulose, and the like, and the hollow fiber membrane is prepared by a non-solvent precipitation gel phase inversion method (NIPS). However, the hollow fiber membrane prepared by the NIPS method has poor strength, and membrane filaments are easy to break in the using process. Researchers also prepare reinforced hollow fiber membranes by a support layer method, but the adhesion performance of resin and the support layer is poor, and defects such as burrs, uneven coating of the membrane layer and the like are easily generated in the preparation process.
Perfluoroethylene propylene (FEP) has outstanding chemical stability, good corrosion resistance, and excellent high and low temperature properties, and is receiving increasing attention from researchers. For example, Xiaochangfa et al, add organic solvent and pore-forming agent, extrude and form, and then stretch by an extraction washing and stretching device to prepare the perfluoropolymer hollow fiber membrane. However, a large amount of organic solvent is used in the preparation method, so that the feeding is difficult in the extrusion process, and the organic solvent is volatile at high temperature, so that the preparation method has higher safety risk and environmental hidden trouble. Therefore, the development of a preparation method of the FEP hollow fiber membrane with green and environment-friendly effects is of great significance.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a green environment-friendly fluorinated ethylene propylene hollow fiber membrane and a preparation method thereof.
The invention provides a preparation method of a fluorinated ethylene propylene hollow fiber membrane, which comprises the following steps:
a) mixing the fluorinated ethylene propylene, a pore-forming agent and a dispersing agent to prepare a fluorinated ethylene propylene hollow fiber;
b) placing the fluorinated ethylene propylene hollow fiber in a closed container, and raising the temperature of the closed container to 270-360 ℃;
c) introducing supercritical carbon dioxide into the closed container until the pressure of the closed container reaches 25-40 MPa, and keeping for a preset time T under the pressure to ensure that the supercritical carbon dioxide is uniformly distributed in the fluorinated ethylene propylene hollow fiber;
d) releasing the pressure of the closed container to foam the supercritical carbon dioxide in the fluorinated ethylene propylene hollow fiber to obtain a fluorinated ethylene propylene hollow fiber primary membrane, wherein the pressure releasing speed of the closed container is greater than or equal to 10MPa/s, and the fluorinated ethylene propylene hollow fiber primary membrane comprises a plurality of first openings;
e) and soaking the perfluorinated ethylene-propylene copolymer hollow fiber primary membrane in an etching solution to etch the pore-forming agent in the perfluorinated ethylene-propylene copolymer hollow fiber primary membrane to form a plurality of second openings, so as to obtain the perfluorinated ethylene-propylene copolymer hollow fiber membrane.
The invention also provides the fluorinated ethylene propylene hollow fiber membrane obtained by the preparation method, the fluorinated ethylene propylene hollow fiber membrane comprises a plurality of openings, the pore size of the openings on the surface of the fluorinated ethylene propylene hollow fiber membrane is 1 nanometer-1 micrometer, the pore size of the openings in the interior of the fluorinated ethylene propylene hollow fiber membrane is 1 nanometer-100 micrometers, and the density of the fluorinated ethylene propylene hollow fiber membrane is 0.5-1.5 g/cm3。
Compared with the prior art, the preparation method carries out secondary pore opening through two different pore opening mechanisms to form the fluorinated ethylene propylene hollow fiber membrane. Specifically, in the step a), polyfluorinated ethylene propylene is uniformly mixed with a pore-forming agent and a dispersing agent, so that the pore-forming agent and the dispersing agent are uniformly distributed in the premix. In the steps c) and d), the perfluoroethylene propylene is changed into a soft phase at a high temperature by raising the temperature of the closed container to 270 ℃ to 360 ℃. When the supercritical carbon dioxide is introduced, the supercritical carbon dioxide is fully dissolved and diffused in the soft-phase fluorinated ethylene propylene. And then, the closed container is subjected to pressure relief at a high pressure relief speed (more than or equal to 10MPa/s), the supercritical carbon dioxide expands and escapes, and the gas breaks through the soft phase of the fluorinated ethylene propylene on the bubble wall to form a plurality of first openings. It is understood that the porogen is partially exposed through the plurality of first openings. In step f), when the fluorinated ethylene propylene hollow fiber primary membrane is soaked in the etching solution, the pore-forming agent on the surface of the fluorinated ethylene propylene hollow fiber primary membrane reacts with the etching solution to form a second opening on the surface of the fluorinated ethylene propylene hollow fiber primary membrane, and at the moment, the etching solution slowly reaches the first opening inside the fluorinated ethylene propylene hollow fiber primary membrane through the second opening on the surface of the fluorinated ethylene propylene hollow fiber primary membrane, and the pore-forming agent exposed through the first opening is etched, so that a plurality of fine second openings are further formed on the inner wall of the first opening. The final fluorinated ethylene propylene hollow fiber membrane comprises a plurality of openings (collectively called the first opening and the second opening). That is, in the production method, the second openings are formed on the basis of the first openings, and the hollow fiber membrane of perfluoroethylene-propylene copolymer obtained by the second openings has a high opening ratio. The preparation method of the fluorinated ethylene propylene hollow fiber membrane has the advantages of simple process, high efficiency, low cost, environmental protection and suitability for industrial production.
The fluorinated ethylene propylene hollow fiber membrane has high aperture ratio, the aperture size of the open pore is moderate (below 100 microns), and the open pore is uniformly distributed. The fluorinated ethylene propylene hollow fiber membrane has good mechanical strength, excellent corrosion resistance and excellent thermal stability, and can be used as a separation membrane to be applied to the fields of water treatment, environmental protection, chemical industry, energy, medicine, food, biology and the like.
Drawings
FIGS. 1 and 2 are Scanning Electron Microscope (SEM) cross-sectional photographs of a fluorinated ethylene propylene hollow fiber membrane obtained in example 1 of the present invention;
FIG. 3 is a surface SEM photograph of a fluorinated ethylene propylene hollow fiber membrane obtained in example 1 of the present invention.
FIGS. 4 and 5 are SEM photographs of the cross section of a fluorinated ethylene propylene hollow fiber membrane obtained in example 2 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The invention provides a preparation method of a fluorinated ethylene propylene hollow fiber membrane, which comprises the following steps:
a) mixing the fluorinated ethylene propylene, a pore-forming agent and a dispersing agent to prepare a fluorinated ethylene propylene hollow fiber;
b) placing the fluorinated ethylene propylene hollow fiber in a closed container, and raising the temperature of the closed container to 270-360 ℃;
c) introducing supercritical carbon dioxide into the closed container until the pressure of the closed container reaches 25-40 MPa, and keeping for a preset time T under the pressure to ensure that the supercritical carbon dioxide is uniformly distributed in the fluorinated ethylene propylene hollow fiber;
d) releasing the pressure of the closed container to foam the supercritical carbon dioxide in the fluorinated ethylene propylene hollow fiber to obtain a fluorinated ethylene propylene hollow fiber primary membrane, wherein the pressure releasing speed of the closed container is greater than or equal to 10MPa/s, and the fluorinated ethylene propylene hollow fiber primary membrane comprises a plurality of first openings;
e) and soaking the perfluorinated ethylene-propylene copolymer hollow fiber primary membrane in an etching solution to etch the pore-forming agent in the perfluorinated ethylene-propylene copolymer hollow fiber primary membrane to form a plurality of second openings, so as to obtain the perfluorinated ethylene-propylene copolymer hollow fiber membrane.
In the step a), the polyfluorinated ethylene propylene, the pore-foaming agent and the dispersing agent can be extruded by a double-screw, single-screw or plunger-type screw extrusion mode to prepare the polyfluorinated ethylene propylene hollow fiber.
The porogen comprises an inorganic carbonate and/or a water soluble polymer. Wherein the inorganic carbonate is at least one of calcium carbonate, magnesium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate and barium carbonate. The water-soluble polymer is polyoxyethylene.
The pore-foaming agent accounts for 1-10% of the premix by mass.
The dispersing agent has the functions of reducing the melt viscosity of the fluorinated ethylene propylene and improving the melt strength of the fluorinated ethylene propylene, so that the subsequent supercritical carbon dioxide can be fully dissolved and diffused in the fluorinated ethylene propylene. The dispersing agent is at least one of stearic acid amide, stearate, oleic acid amide, erucamide and ethylene bis-stearamide, and the mass of the dispersing agent is 0.1-1% of that of the premix. The dispersant is volatilized during the subsequent pressure relief step d) and, of course, is dissolved in the etching solution during step e) and is removed therefrom.
In the step b), the temperature in the closed container is increased to enable the perfluoroethylene-propylene copolymer hollow fiber to be in a special soft phase state which is not completely fluid, and the perfluoroethylene-propylene copolymer hollow fiber can still maintain the hollow fiber state, so that the supercritical carbon dioxide in the step c is favorably dissolved in the perfluoroethylene-propylene copolymer hollow fiber and is uniformly distributed. It will be appreciated that the "dissolution" is not intended to be a general dissolution of salt in water in the true sense, but rather a particular state of dissolution. The perfluorinated ethylene-propylene copolymer hollow fiber is in a soft phase due to the temperature rise of the closed container, so that supercritical carbon dioxide can be uniformly dissolved and diffused in the perfluorinated ethylene-propylene copolymer hollow fiber within a short preset time T (more than or equal to 8 minutes); this saves time greatly and improves the production efficiency.
The temperature in the closed container may be set according to the specific type of the fluorinated ethylene propylene, as long as the fluorinated ethylene propylene is in a soft phase. The lower limit temperature of 270 ℃ in the closed container is higher than the glass transition temperature of the fluorinated ethylene propylene, so that the fluorinated ethylene propylene is in a soft phase; the upper limit temperature of the closed container is not enough to cause full melting of the fluorinated ethylene propylene in terms of the upper limit temperature of 360 ℃ in the closed container.
The closed vessel may be an autoclave. Before raising the temperature of the closed container, introducing carbon dioxide into the closed container to remove air in the closed container.
In the step c), supercritical carbon dioxide can be introduced into the closed container until the pressure of the closed container reaches 25MPa to 40MPa, and then a plurality of first openings with consistent pore sizes and micron-level pore sizes can be obtained through the foaming process in the step d).
In the step d), when the closed container is depressurized at a high depressurization rate (greater than or equal to 10MPa/s), the supercritical carbon dioxide expands and escapes, and the gas breaks through the soft phase of the fluorinated ethylene propylene on the bubble wall to form a plurality of first openings. It is understood that the porogen is partially exposed through the plurality of first openings.
Preferably, the pressure relief rate of the closed container is 15MPa/s or more, and in this case, a plurality of first openings having a more uniform pore size and a pore size of micrometer level are obtained after foaming.
In step e), when the fluorinated ethylene propylene hollow fiber membrane is immersed in the etching solution, the porogen on the surface of the fluorinated ethylene propylene hollow fiber membrane reacts with the etching solution to form a second opening on the surface of the fluorinated ethylene propylene hollow fiber membrane, and the etching solution slowly reaches the first opening inside the fluorinated ethylene propylene hollow fiber membrane through the second opening on the surface of the fluorinated ethylene propylene hollow fiber membrane, and the porogen exposed through the first opening is etched, so that a plurality of fine second openings are further formed on the inner wall of the first opening. The final fluorinated ethylene propylene hollow fiber membrane comprises a plurality of openings (collectively called the first opening and the second opening). That is, in the production method, the second openings are formed on the basis of the first openings, and the hollow fiber membrane of perfluoroethylene-propylene copolymer obtained by the second openings has a high opening ratio. The pore size of the open pores is moderate (below 100 microns).
The etching solution is an acidic solution or water. The acidic solution is at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid and citric acid. When the pore-forming agent is inorganic carbonate, the etching solution selects an acidic solution, and the inorganic carbonate is dissolved and chemically etched by utilizing the reaction between the inorganic carbonate and the acidic solution to form second openings. When the pore-foaming agent is water-soluble polymer polyoxyethylene, the etching solution can be water or acid solution, and the polyoxyethylene can be dissolved in water to be physically etched to form a second opening.
The molar solubility of the acidic solution is not limited, but is preferably 1.5mol/L to 4.0 mol/L. The soaking time of the fluorinated ethylene propylene hollow fiber primary membrane in the etching solution is 1-72 hours, preferably 1-24 hours. The soaking process may be performed at room temperature.
Further, before the perfluoroethylene-propylene copolymer hollow fiber primary membrane is soaked in an etching solution, the method further comprises the step of stretching the perfluoroethylene-propylene copolymer hollow fiber primary membrane. The stretching medium is water, the stretching temperature range is 40-80 ℃, and the stretching ratio is 1.5-5 times.
Furthermore, after the perfluorinated ethylene-propylene copolymer hollow fiber primary membrane is soaked in the etching solution, a step of water extraction and washing can be performed to remove impurities such as the residual etching solution in the perfluorinated ethylene-propylene copolymer hollow fiber primary membrane. The temperature range of the water extraction and washing process is 20-90 ℃, and the time is 0.5-48 hours.
It should be noted that the pore diameter of the open pores on the surface of the resulting polyperfluoroethylene propylene hollow fiber membrane is smaller than the pore diameter of the open pores inside the polyperfluoroethylene propylene hollow fiber membrane. The perfluorinated ethylene propylene copolymer hollow fiber primary membrane obtained in the step e) is similar to steamed bread in life after evaporation, the inner opening is large, and the surface is basically provided with no holes.
The invention also provides the fluorinated ethylene propylene hollow fiber membrane prepared by the preparation method. The fluorinated ethylene propylene hollow fiber membrane comprises a plurality of openings. The opening is a general term for the first opening and the second opening. The plurality of openings are communicated with each other. The walls of the openings are thin.
Referring to fig. 1 to 2, the cross section of the fluorinated ethylene propylene hollow fiber membrane is a sponge-like cell with uniformly distributed pores, and the inner and outer skin layers are thin. The pore size of the open pore on the surface of the fluorinated ethylene-propylene hollow fiber membrane is 1 nanometer to 1 micrometer, the pore size of the open pore inside the fluorinated ethylene-propylene hollow fiber membrane is 1 nanometer to 100 micrometers, and the density of the fluorinated ethylene-propylene hollow fiber membrane is 0.5 to 1.5g/cm3。
The fluorinated ethylene propylene hollow fiber membrane has high aperture ratio, good mechanical strength, excellent corrosion resistance and excellent thermal stability, and can be used as a separation membrane to be applied to the fields of water treatment, environmental protection, chemical industry, energy, medicine, food, biology and the like.
The preparation method of the fluorinated ethylene propylene hollow fiber membrane has the advantages of simple process, high efficiency, low cost, environmental protection and suitability for industrial production.
The following description will be made with reference to specific examples of the preparation method of the fluorinated ethylene propylene hollow fiber membrane of the present invention:
example 1
Step (1), 945g of Fluorinated Ethylene Propylene (FEP), 50g of calcium carbonate and 5g of stearic acid amide are uniformly mixed, and melt-extruded by a double-screw extruder to prepare FEP hollow fiber, wherein the extrusion temperature is 300-330 ℃.
And (2) placing the FEP hollow fiber in an autoclave connected with a supercritical carbon dioxide device, introducing carbon dioxide, and purging for 4 minutes at low pressure. The autoclave temperature was set at 315 ℃.
Step (3) introducing supercritical carbon dioxide fluid until the pressure in the kettle reaches 30MPa after the temperature is reached; the constant temperature and pressure were maintained for 20 minutes.
And (4) opening a pressure relief valve of the high-pressure kettle, and relieving the pressure to normal pressure at the speed of 15MPa/s to obtain the FEP hollow fiber primary membrane.
Step (5), soaking the FEP hollow fiber primary membrane in a 2% dilute hydrochloric acid solution for 48 hours; and then putting the hollow fiber membrane into deionized water for immersion cleaning for 24 hours at the temperature of 60 ℃, and oscillating to obtain the FEP hollow fiber membrane.
Referring to fig. 1 and fig. 2, the cross section of the FEP hollow fiber membrane has a plurality of micropores uniformly distributed. The average pore diameter of micropores of the section of the FEP hollow fiber membrane is tested to be 13.9 mu m, and the average thicknesses of the inner skin layer and the outer skin layer are respectively 2.6 mu m and 1.7 mu m.
Referring to fig. 3, a plurality of micropores are distributed on the surface of the FEP hollow fiber membrane.
Example 2
The FEP hollow fiber membrane of this example was produced in substantially the same manner as in example 1, except that the FEP hollow fiber primary membrane was subjected to a stretching treatment at a stretching ratio of 2 times, a stretching medium of water, and a stretching temperature of 70 ℃ before being immersed in dilute hydrochloric acid in step (5).
Referring to FIGS. 4 and 5, the average pore diameter of micropores in the cross section of the FEP hollow fiber membrane was 11.3 μm, and the average thicknesses of the inner and outer skin layers were 1.9 μm and 1.1. mu.m, respectively.
While the foregoing is directed to the preferred embodiment of the present invention, it will be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (8)
1. A preparation method of a fluorinated ethylene propylene hollow fiber membrane comprises the following steps:
a) mixing the fluorinated ethylene propylene, a pore-forming agent and a dispersing agent to prepare a fluorinated ethylene propylene hollow fiber;
b) placing the fluorinated ethylene propylene hollow fiber in a closed container, and raising the temperature of the closed container to 270-360 ℃;
c) introducing supercritical carbon dioxide into the closed container until the pressure of the closed container reaches 25-40 MPa, and keeping for a preset time T under the pressure to ensure that the supercritical carbon dioxide is uniformly distributed in the fluorinated ethylene propylene hollow fiber;
d) releasing the pressure of the closed container to foam the supercritical carbon dioxide in the fluorinated ethylene propylene hollow fiber to obtain a fluorinated ethylene propylene hollow fiber primary membrane, wherein the pressure releasing speed of the closed container is greater than or equal to 10MPa/s, and the fluorinated ethylene propylene hollow fiber primary membrane comprises a plurality of first openings;
e) and soaking the perfluorinated ethylene-propylene copolymer hollow fiber primary membrane in an etching solution to etch the pore-forming agent in the perfluorinated ethylene-propylene copolymer hollow fiber primary membrane to form a plurality of second openings, so as to obtain the perfluorinated ethylene-propylene copolymer hollow fiber membrane.
2. The method for preparing a fluorinated ethylene propylene hollow fiber membrane according to claim 1, wherein the dispersant in step a) is at least one of stearic acid amide, stearate, oleic acid amide, erucamide and ethylene bis-stearamide, and the dispersant accounts for 0.1-1% of the mass of the premix.
3. The preparation method of the fluorinated ethylene propylene hollow fiber membrane according to claim 1, wherein the pore-forming agent in step a) comprises an inorganic carbonate and/or a water-soluble polymer, wherein the inorganic carbonate is at least one of calcium carbonate, magnesium carbonate, sodium bicarbonate, sodium carbonate, potassium carbonate and barium carbonate, and the water-soluble polymer is polyoxyethylene.
4. The preparation method of the fluorinated ethylene propylene hollow fiber membrane according to claim 1, wherein the pore-forming agent accounts for 1-10% of the premix in the step a).
5. A method for preparing a fluorinated ethylene propylene hollow fiber membrane according to claim 1, wherein the predetermined time T in step c) is 10 minutes or more.
6. The method for preparing a fluorinated ethylene propylene hollow fiber membrane according to claim 1, wherein the etching solution in step e) is an acidic solution or water, and the acidic solution is at least one of sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid, acetic acid and citric acid.
7. A method of preparing a perfluoroethylene-propylene hollow fiber membrane according to claim 1, further comprising a step of stretching the perfluoroethylene-propylene hollow fiber membrane before soaking the perfluoroethylene-propylene hollow fiber membrane in an etching solution in step e).
8. A fluorinated ethylene propylene hollow fiber membrane obtained by the production method according to any one of claims 1 to 7, wherein the fluorinated ethylene propylene hollow fiber membrane comprises a plurality of openings, the size of the openings on the surface of the fluorinated ethylene propylene hollow fiber membrane is 1 nm to 1 μm, and the fluorinated ethylene propylene hollow fiber membrane has a pore sizeThe pore size of the open pore inside the hollow fiber membrane is 1 nanometer to 100 micrometers, and the density of the fluorinated ethylene propylene hollow fiber membrane is 0.5 to 1.5g/cm3。
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