CN103183884A - Fluoride-containing microporous membrane and preparation method thereof - Google Patents
Fluoride-containing microporous membrane and preparation method thereof Download PDFInfo
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- CN103183884A CN103183884A CN2011104457385A CN201110445738A CN103183884A CN 103183884 A CN103183884 A CN 103183884A CN 2011104457385 A CN2011104457385 A CN 2011104457385A CN 201110445738 A CN201110445738 A CN 201110445738A CN 103183884 A CN103183884 A CN 103183884A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a microporous membrane material, particularly relates to a fluorine-containing microporous membrane and a preparation method thereof, and belongs to the technical field of membrane. The fluorine-containing microporous membrane is prepared by melt-extrusion, biaxial stretching and heat setting of a fluorine-containing polymer, wherein the fluorine-containing polymer is a modified vinyl fluoride resin. The modified vinyl fluoride resin is prepared by polymerizing vinyl fluoride, ethylene and fluorine-containing functional monomers. The prepared membrane has a thickness of 0.1-20 microns, a pore size of 0.1-10 microns, and a porosity of 70-97%. The microporous membrane prepared by the invention is excellent in overall performance, good in compatibility with the enhanced material, and enhanced in adhesion between layers, and the preparation method is simple and easy to operate.
Description
Technical field
The present invention relates to a kind of microporous membrane material, particularly a kind of fluorine-containing microporous membrane and preparation method thereof belongs to the membrane technique field, and this microporous membrane can be used for the strongthener of proton fuel cell and chlor-alkali ionic membrane.
Background technology
After the perfluor ion-exchange composite membranes was exhibited one's skill to the full in chlorine industry, the whole world that is applied in of perfluorinated ion-exchange membrane had obtained research widely.No matter perfluorinated ion-exchange membrane is in chlorine industry or the application in fuel cell, technique known all needs to adopt the enhancing framework material to strengthen at present, no matter be to adopt poromerics to strengthen or fiber reinforcement, these strongtheners are a spot of sacrificial fiber material of tetrafluoroethylene, meltable poly and auxiliary usefulness nothing more than.The strongthener of these perfluor types belongs to the insulating material of no ion exchanging function, its volume specific resistance will exceed more than 14 orders of magnitude with the resistivity of perfluor type ion-exchange than general chlorine industry, thereby at the directed back side that sees through film of positively charged ion " blind area " will appear, the corresponding useful area that reduces the cation permeation film, increased membrane resistance and bath voltage, this is a technical barrier of present this area; The another one technical barrier is no matter tetrafluoroethylene or meltable poly, all be to have very low surface energy, adhesion property is very poor, a little less than the interlayer adhesion of itself and exchange membrane material, in the use between rete easily off, peel off, shorten the work-ing life of mould material.
The strongthener of using in the fuel cell mainly is microporous teflon membran at present, owing to the strong-hydrophobicity of microporous teflon membran and the strong absorptive of resin solution, causes the loading level deficiency of resin, influences the performance of film.Though a lot of researchs all have no idea fundamentally to address this problem by surface modification and the filling-modified microporous teflon membran water-absorbent that improves of blend of tetrafluoroethylene.And because tetrafluoroethylene viscosity up to melting temperature the time is still very big, can not melt-processed, the whole operation of preparation microporous membrane comparatively bothers.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of fluorine-containing microporous membrane and preparation method thereof, this microporous membrane high comprehensive performance and good with the material compatibility that is enhanced has strengthened the cohesiveness between layer and the layer.
Described fluorine-containing microporous membrane, be by fluoropolymer through melt extrude, two-way stretch and heat setting type is prepared from, wherein fluoropolymer is the modification fluoroethylene resin, the modification fluoroethylene resin is formed by vinyl fluoride, ethene and functional fluoropolymer monomer polymerization, the film thickness of preparing is 0.1～20 micron, the aperture is 0.1～10 micron, and porosity is 70～97%.
Described fluoropolymer is a kind of modification fluoroethylene resin that can melt-processed, have good high temperature resistant, wear-resisting, with performances such as other materials cohesive strength height.
The content of described vinyl fluoride in the modification fluoroethylene resin is 60～95mol%, and preferred content is 65～80mol%.
The content of described ethene in the modification fluoroethylene resin is 1～15mol%, and preferred content is 3～10mol%.
The general formula of described functional fluoropolymer monomer is as follows:
(1) CF
2=CXY, wherein X, Y all be-H ,-F or-a kind of among the Cl, its content in the modification fluoroethylene resin is 0～30mol%, preferred content is 3～15mol%;
(2) CF
2=CFR
f, R
fA kind of in perfluoroalkyl or the perfluoro alkoxy, its content in the modification fluoroethylene resin is 0～15mol%, preferred content is 3～10mol%;
Above-mentioned two kinds of monomers (1) and the content of monomer (2) in the modification fluoroethylene resin are not 0 simultaneously.
Described CF
2=CXY is vinylidene, trifluorochloroethylene, tetrafluoroethylene or trifluoro-ethylene, preferred trifluorochloroethylene or vinylidene.
CF
2=CFR
fRepresentative contains 3 carbon above perfluoroolefine or perfluor alkene ether monomer, comprises R 1216, perfluoro methyl vinyl ether, perfluoroethylvinyl ether or perfluoro propyl vinyl ether, wherein is preferably R 1216 or perfluoro propyl vinyl ether.
The preparation method of described modification fluoroethylene resin, under the initiator effect by monomer vinyl fluoride (CFH=CH
2), ethene (C
2H
4), CF
2=CXY, CF
2=CFR
fCarry out copolymerization, this polyreaction is carried out or is carried out in emulsion at aqueous phase, 40～100 ℃ of temperature of reaction, reaction pressure 1～10MPa, 1～15 hour reaction times.
Wherein, described initiator is selected from one or more in azo-compound, organo-peroxide, inorganic peroxide, basic metal persulfide or the alkaline-earth metal persulfide;
Preferably, described initiator is selected from: azo diisobutyl amidine dihydrochloride, Diisopropyl azodicarboxylate, benzoyl peroxide, tertbutyl peroxide, Potassium Persulphate, ammonium persulphate or antihypo.
Described initiator amount is no more than the 0.05wt.% of total inventory.Decide according to prior art.
When polyreaction was carried out at aqueous phase, wherein the content of water was 60～95wt.%, and the content of resulting polymers is 5～40wt.%, and the content of preferred polymers is 10～20wt.%.
The preparation method of described modification fluoroethylene resin also can adopt letex polymerization, and the emulsifying agent of wherein selecting for use can be any emulsifying agent that is generally used in the fluoropolymer preparation process.Emulsifying agent commonly used comprises ionic emulsifying agent and nonionic emulsifier.Ionic emulsifying agent comprises sodium soap, sodium lauryl sulphate, alkyl sodium sulfonate, sodium alkylarysulfonate, perfluoro alkyl sulfonic acid sodium, ammonium perfluorocaprylate etc., nonionic emulsifier comprises the alkyl phenol polyether alcohols, as polyoxyethylene nonylphenol ether, polyoxyethylene fatty acid, polyoxyethylene fatty acid ether.Mentioned emulsifier can use separately, also can multiple composite use.Emulsifying agent is preferably ammonium perfluorocaprylate, perfluorinated sulfonic acid sodium, sodium laurylsulfonate, one or more among the polyoxyethylene nonylphenol ether NP-10.Emulsifying agent prepares prior art by fluoropolymer and gets final product.
What clearly do not limit among the preparation method all can realize with reference to this area routine techniques.
The preparation method of described fluorine-containing microporous membrane is characterized in that may further comprise the steps:
(1) melt extrude basement membrane: with the modification fluoroethylene resin at 100～250 ℃, by melt extruding the preparation basement membrane;
(2) two-way stretch: the basement membrane of step (1) preparation is carried out two-way stretch at 100～200 ℃, and rate of extension is 1～20m/min, and draw ratio is 1～500;
(3) heat setting type: with the biaxial stretching film of step (2) preparation 170～250 ℃ of heat setting types 20～100 seconds.
Preferred 120～190 ℃ of the described two-way stretch temperature of step (2).
Preferred 1～the 15m/min of the described rate of extension of step (2).
Preferred 2～200 times of the described draw ratio of step (2).
Preferred 190～230 ℃ of the described heat setting temperature of step (3).
Preferred 30～60 seconds of the described heat-setting time of step (3).
The described two-way stretch of step (2) is that synchronous bidirectional stretches or the substep two-way stretch.
The synchronous bidirectional stretching refers to vertical, horizontal and stretches simultaneously, and rate of extension can be identical, also can be different, and draw ratio can be identical, also can be different.
The substep two-way stretch refers to first longitudinal stretching, cross directional stretch again, and rate of extension can be identical, also can be different, draw ratio can be identical, also can be different.
Beneficial effect of the present invention is as follows:
The present invention with the modification fluoroethylene resin of melt-processable through melt extruding, the prepared of two-way stretch and heat setting type becomes that thickness is even, the aperture evenly, the microporous membrane of dimensional stabilizing, this microporous membrane high comprehensive performance and good with the material compatibility that is enhanced has strengthened the cohesiveness between layer and the layer; And preparation is simple, easy to implement.
Embodiment
Be described further below in conjunction with the present invention of embodiment.
The modification vinyl fluoride all prepares according to following steps among the embodiment 1～8:
1, the perfluoro ammonium caprylate aqueous solution that deionized water and the 50g concentration of 6L is 20wt.% adds polymeric kettle, stirs and is warming up to 90 ℃.
2, the copolyreaction monomer is added reactor in proportion, make reactor reach reaction pressure 2.1MPa.
3, adding the 2g ammonium persulphate by volume pump is dissolved in the 1L deionized water and is mixed with initiator solution, begin reaction, in reaction process, change along with the carrying out of reaction in order to guarantee that monomer is not formed in the reactor, in reactor, add mix monomer in proportion, keep the reactor constant pressure, add an amount of initiator solution simultaneously.Reacted 2 hours, unreacted monomer is emitted in cooling, and the material that obtains washs through separating, and drying obtains the modification fluoride copolymers.
Embodiment 1
In the modification fluoroethylene resin that described fluorine-containing microporous membrane preparation is adopted: vinyl fluoride content is 89mol%, ethene C
2H
4Content is 5.5mol%, and trifluorochloroethylene content is 4.5%.
The preparation method of described fluorine-containing microporous membrane is as follows:
(1) melt extrude basement membrane: be 170 ℃ with this fluoro-resin at extruder temperature, die head temperature is under 190 ℃ the condition, by melt extruding the basement membrane of preparation two-way stretch.
(2) two-way stretch: with the basement membrane cooling of preparation, and 100 ℃ carry out substep in length and breadth two-way stretch once, longitudinal stretching speed is 5m/min, cross directional stretch speed is 2m/min, draw ratio is 10.
(3) heat setting type: the biaxial stretching film of step (2) preparation is carried out heat setting type, at 200 ℃ of heat setting type 30s.
Zhi Bei microporous membrane thickness is 15 microns as stated above, and thickness is even, and the aperture is 5 microns, and porosity is 75%, and the aperture is even, and dimensional stability is good.
Embodiment 2
In the modification fluoroethylene resin that described fluorine-containing microporous membrane preparation is adopted: vinyl fluoride content is 60mol%, ethene C
2H
4Content is 15mol%, and vinylidene content is 25mol%.
The preparation method of described fluorine-containing microporous membrane is as follows:
(1) melt extrude basement membrane: be 190 ℃ with this fluoro-resin at extruder temperature, die head temperature is under 220 ℃ the condition, by melt extruding the basement membrane of preparation two-way stretch.
(2) two-way stretch: with the basement membrane cooling of preparation, and 150 ℃ carry out substep in length and breadth two-way stretch respectively once, longitudinal stretching speed is 15m/min, draw ratio is 100, cross directional stretch speed is 10m/min, draw ratio is 60.
(3) heat setting type: the biaxial stretching film of step (2) preparation is carried out heat setting type, at 220 ℃ of heat setting type 50s.
Zhi Bei microporous membrane thickness is 5 microns as stated above, and thickness is even, and the aperture is 0.2 micron, and porosity is 80%, and the aperture is even, and dimensional stability is good.
Embodiment 3
In the modification fluoroethylene resin that described fluorine-containing microporous membrane preparation is adopted: vinyl fluoride content is 75.8mol%, ethene C
2H
4Content is 14.2%, for R 1216 content is 10mol%.
The preparation method of described fluorine-containing microporous membrane is as follows:
(1) melt extrude basement membrane: be 190 ℃ with this fluoro-resin at extruder temperature, die head temperature is under 220 ℃ the condition, by melt extruding the basement membrane of preparation two-way stretch.
(2) two-way stretch: the basement membrane of preparation is cooled off, and carry out synchronously two-way stretch in length and breadth once at 150 ℃.Be 10m/min to rate of extension in length and breadth, draw ratio is 20.
(3) heat setting type: the biaxial stretching film of step (2) preparation is carried out heat setting type, at 190 ℃ of heat setting type 50s.
Zhi Bei microporous membrane thickness is 0.1 micron as stated above, and thickness is even, and the aperture is 10 microns, and porosity is 81%, and the aperture is even, and dimensional stability is good.
Embodiment 4
In the modification fluoroethylene resin that described fluorine-containing microporous membrane preparation is adopted: vinyl fluoride content is 81.5mol%, ethene C
2H
4Content is 15%, for perfluoro propyl vinyl ether content is 3.5mol%.
The preparation method of described fluorine-containing microporous membrane is as follows:
(1) melt extrude basement membrane: be 180 ℃ with this fluoro-resin at extruder temperature, die head temperature is under 210 ℃ the condition, by melt extruding the basement membrane of preparation two-way stretch.
(2) two-way stretch: the basement membrane of preparation is cooled off, and carry out synchronously two-way stretch in length and breadth once at 200 ℃.Be 5m/min to rate of extension in length and breadth, draw ratio is 150.
(3) heat setting type: the biaxial stretching film of step (2) preparation is carried out heat setting type, at 210 ℃ of heat setting type 80s.
Zhi Bei microporous membrane thickness is 0.8 micron as stated above, and thickness is even, and the aperture is 0.1 micron, and porosity is 89%, and the aperture is even, and dimensional stability is good.
Embodiment 5
In the modification fluoroethylene resin that described fluorine-containing microporous membrane preparation is adopted: vinyl fluoride content is 79mol%, ethene C
2H
4Content is 8.3mol%, and trifluorochloroethylene content is 7.2mol%, and R 1216 content is 5.5mol%.
The preparation method of described fluorine-containing microporous membrane is as follows:
(1) melt extrude basement membrane: be 180 ℃ with this fluoro-resin at extruder temperature, die head temperature is under 220 ℃ the condition, by melt extruding the basement membrane of preparation two-way stretch.
(2) two-way stretch: the basement membrane of preparation is cooled off, and carry out synchronously two-way stretch in length and breadth once at 170 ℃.Longitudinal stretching speed is 20m/min, and cross directional stretch speed is 8m/min, and draw ratio is 80.
(3) heat setting type: the biaxial stretching film of step (2) preparation is carried out heat setting type, at 210 ℃ of heat setting type 60s.
Zhi Bei microporous membrane thickness is 7 microns as stated above, and thickness is even, and the aperture is 0.5 micron, and porosity is 93%, and the aperture is even, and dimensional stability is good.
Embodiment 6
In the modification fluoroethylene resin that described fluorine-containing microporous membrane preparation is adopted: vinyl fluoride content is 65.6mol%, ethene C
2H
4Content is 9.4mol%, and trifluorochloroethylene content is 14.3mol%, and perfluoro propyl vinyl ether content is 10.7mol%.
The preparation method of described fluorine-containing microporous membrane is as follows:
(1) melt extrude basement membrane: be 180 ℃ with this fluoro-resin at extruder temperature, die head temperature is under 190 ℃ the condition, by melt extruding the basement membrane of preparation two-way stretch.
(2) two-way stretch: the basement membrane of preparation is cooled off, and carry out step drawing respectively once at 100 ℃, longitudinal stretching speed is 7m/min, and cross directional stretch speed is 2m/min, and draw ratio is 15.
(3) heat setting type: the biaxial stretching film of step (2) preparation is carried out heat setting type, at 200 ℃ of heat setting type 30s.
Zhi Bei microporous membrane thickness is 13 microns as stated above, and thickness is even, and the aperture is 3 microns, and porosity is 85%, and the aperture is even, and dimensional stability is good.
Embodiment 7
In the modification fluoroethylene resin that described fluorine-containing microporous membrane preparation is adopted: vinyl fluoride content is 77.1mol%, ethene C
2H
4Content is 8.8mol%, and vinylidene content is 8.4mol%, and R 1216 content is 5.7mol%.
The preparation method of described fluorine-containing microporous membrane is as follows:
(1) melt extrude basement membrane: be 190 ℃ with this fluoro-resin at extruder temperature, die head temperature is under 220 ℃ the condition, by melt extruding the basement membrane of preparation two-way stretch.
(2) two-way stretch: the basement membrane of preparation is cooled off, and carry out synchronously two-way stretch in length and breadth once at 150 ℃.Be 10m/min to rate of extension in length and breadth, draw ratio is 10.
(3) heat setting type: the biaxial stretching film of step (2) preparation is carried out heat setting type, at 180 ℃ of heat setting type 50s.
Zhi Bei microporous membrane thickness is 0.6 micron as stated above, and thickness is even, and the aperture is 8 microns, and porosity is 78%, and the aperture is even, and dimensional stability is good.
Embodiment 8
In the modification fluoroethylene resin that described fluorine-containing microporous membrane preparation is adopted: vinyl fluoride content is 87.7mol%, ethene C
2H
4Content is 7.3mol%, and vinylidene content is 4.5mol%, and perfluoro propyl vinyl ether content is 3.5mol%.
The preparation method of described fluorine-containing microporous membrane is as follows:
(1) melt extrude basement membrane: be 170 ℃ with this fluoro-resin at extruder temperature, die head temperature is under 210 ℃ the condition, by melt extruding the basement membrane of preparation two-way stretch.
(2) two-way stretch: the basement membrane of preparation is cooled off, and carry out synchronously two-way stretch in length and breadth once at 150 ℃.Be 20m/min to rate of extension in length and breadth, draw ratio is 30.
(3) heat setting type: the biaxial stretching film of step (2) preparation is carried out heat setting type, at 190 ℃ of heat setting type 50s.
Zhi Bei microporous membrane thickness is 0.1 micron as stated above, and thickness is even, 0.1 micron in aperture, and porosity is 87%, and the aperture is even, dimensional stability is good.
Claims (10)
1. fluorine-containing microporous membrane, it is characterized in that: by fluoropolymer through melt extrude, two-way stretch and heat setting type is prepared from, wherein fluoropolymer is the modification fluoroethylene resin, the modification fluoroethylene resin is formed by vinyl fluoride, ethene and functional fluoropolymer monomer polymerization, the film thickness of preparing is 0.1～20 micron, the aperture is 0.1～10 micron, and porosity is 70～97%.
2. want 1 described fluorine-containing microporous membrane according to right, it is characterized in that the content of described vinyl fluoride in the modification fluoroethylene resin is 60～95mol%.
3. want 1 described fluorine-containing microporous membrane according to right, it is characterized in that the content of described ethene in the modification fluoroethylene resin is 1～15mol%.
4. wants 1 described fluorine-containing microporous membrane according to right, it is characterized in that the general formula of described functional fluoropolymer monomer is as follows, and the content of two kinds of monomers in the modification fluoroethylene resin is not 0 simultaneously:
(1) CF
2=CXY, wherein X, Y all be-H ,-F or-a kind of among the Cl, its content in the modification fluoroethylene resin is 0～30mol%;
(2) CF
2=CFR
f, R
fA kind of in perfluoroalkyl or the perfluoro alkoxy, its content in the modification fluoroethylene resin is 0～15mol%.
5. want 4 described fluorine-containing microporous membranes according to right, it is characterized in that described CF
2=CXY is vinylidene, trifluorochloroethylene, tetrafluoroethylene or trifluoro-ethylene.
6. want 5 described fluorine-containing microporous membranes according to right, it is characterized in that described CF
2=CXY is vinylidene or trifluorochloroethylene.
7. want 4 described fluorine-containing microporous membranes according to right, it is characterized in that described CF
2=CFR
fBe R 1216, perfluoro methyl vinyl ether, perfluoroethylvinyl ether or perfluoro propyl vinyl ether.
8. want 7 described fluorine-containing microporous membranes according to right, it is characterized in that described CF
2=CFR
fBe R 1216 or perfluoro propyl vinyl ether.
9. the preparation method of the arbitrary described fluorine-containing microporous membrane of claim 1～8 is characterized in that may further comprise the steps:
(1) melt extrude basement membrane: with the modification fluoroethylene resin at 100～250 ℃, by melt extruding the preparation basement membrane;
(2) two-way stretch: the basement membrane of step (1) preparation is carried out two-way stretch at 100～200 ℃, and rate of extension is 1～20m/min, and draw ratio is 1～500 times;
(3) heat setting type: with the biaxial stretching film of step (2) preparation 170～250 ℃ of heat setting types 20～100 seconds.
10. the preparation method of fluorine-containing microporous membrane according to claim 9 is characterized in that the described two-way stretch of step (2) is that synchronous bidirectional stretches or the substep two-way stretch.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752189A (en) * | 2014-01-17 | 2014-04-30 | 山东东岳高分子材料有限公司 | Preparation method of microporous membrane with ion exchange function |
| CN107325238A (en) * | 2017-06-20 | 2017-11-07 | 浙江汉丞科技有限公司 | A kind of fluorine-containing superoleophobic microporous barrier and its application |
| CN107353374A (en) * | 2017-06-20 | 2017-11-17 | 浙江汉丞科技有限公司 | A kind of fluorine-containing compound for fluorine-containing superoleophobic microporous barrier |
| CN113043632A (en) * | 2021-03-09 | 2021-06-29 | 山东森荣新材料股份有限公司 | Preparation method of polytetrafluoroethylene high-strength microporous membrane |
| CN114272770A (en) * | 2021-12-24 | 2022-04-05 | 苏州名列膜材料有限公司 | Polytetrafluoroethylene microporous membrane, preparation method and application thereof |
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| JPS596231A (en) * | 1982-07-05 | 1984-01-13 | Mitsubishi Rayon Co Ltd | Porous fluorocarbon resin membrane and its production |
| CN102186909A (en) * | 2008-10-16 | 2011-09-14 | 旭硝子株式会社 | Process for producing porous ethylene/tetrafluoroethylene copolymer and porous ethylene/tetrafluoroethylene copolymer |
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| JPS596231A (en) * | 1982-07-05 | 1984-01-13 | Mitsubishi Rayon Co Ltd | Porous fluorocarbon resin membrane and its production |
| CN102186909A (en) * | 2008-10-16 | 2011-09-14 | 旭硝子株式会社 | Process for producing porous ethylene/tetrafluoroethylene copolymer and porous ethylene/tetrafluoroethylene copolymer |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752189A (en) * | 2014-01-17 | 2014-04-30 | 山东东岳高分子材料有限公司 | Preparation method of microporous membrane with ion exchange function |
| CN103752189B (en) * | 2014-01-17 | 2015-12-30 | 山东东岳高分子材料有限公司 | A kind of preparation method with the microporous barrier of ion exchanging function |
| CN107325238A (en) * | 2017-06-20 | 2017-11-07 | 浙江汉丞科技有限公司 | A kind of fluorine-containing superoleophobic microporous barrier and its application |
| CN107353374A (en) * | 2017-06-20 | 2017-11-17 | 浙江汉丞科技有限公司 | A kind of fluorine-containing compound for fluorine-containing superoleophobic microporous barrier |
| CN107325238B (en) * | 2017-06-20 | 2019-11-05 | 浙江汉丞科技有限公司 | The fluorine-containing superoleophobic microporous barrier of one kind and its application |
| CN107353374B (en) * | 2017-06-20 | 2019-11-05 | 浙江汉丞科技有限公司 | A kind of fluorine-containing mixture for fluorine-containing superoleophobic microporous barrier |
| CN113043632A (en) * | 2021-03-09 | 2021-06-29 | 山东森荣新材料股份有限公司 | Preparation method of polytetrafluoroethylene high-strength microporous membrane |
| CN114272770A (en) * | 2021-12-24 | 2022-04-05 | 苏州名列膜材料有限公司 | Polytetrafluoroethylene microporous membrane, preparation method and application thereof |
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|---|---|
| CN103183884B (en) | 2015-07-15 |
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