CN103386256A - Method for preparing hollow fiber membranes and tubular membranes with microporous PTFE hybrid flat membrane wrapping method - Google Patents
Method for preparing hollow fiber membranes and tubular membranes with microporous PTFE hybrid flat membrane wrapping method Download PDFInfo
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- CN103386256A CN103386256A CN2013102489855A CN201310248985A CN103386256A CN 103386256 A CN103386256 A CN 103386256A CN 2013102489855 A CN2013102489855 A CN 2013102489855A CN 201310248985 A CN201310248985 A CN 201310248985A CN 103386256 A CN103386256 A CN 103386256A
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- 239000012528 membrane Substances 0.000 title claims abstract description 111
- 229920001343 polytetrafluoroethylene Polymers 0.000 title claims abstract description 78
- 239000004810 polytetrafluoroethylene Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 239000011347 resin Substances 0.000 claims abstract description 14
- 229920005989 resin Polymers 0.000 claims abstract description 14
- 239000002033 PVDF binder Substances 0.000 claims abstract description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 41
- 239000011148 porous material Substances 0.000 claims description 29
- 239000000835 fiber Substances 0.000 claims description 25
- 229920006361 Polyflon Polymers 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 239000000314 lubricant Substances 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 239000003350 kerosene Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010687 lubricating oil Substances 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract description 2
- 238000003490 calendering Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 abstract 1
- 230000008023 solidification Effects 0.000 abstract 1
- 238000007711 solidification Methods 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 71
- 239000000463 material Substances 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000004809 Teflon Substances 0.000 description 2
- 229920006362 Teflon® Polymers 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920004933 Terylene® Polymers 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000001998 anti-microbiological effect Effects 0.000 description 1
- 239000010425 asbestos Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 235000012489 doughnuts Nutrition 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052895 riebeckite Inorganic materials 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a method for preparing hollow fiber membranes and tubular membranes with a microporous PTFE hybrid flat membrane wrapping method. Dispersed PTFE resin and polyvinylidene fluoride resin are mixed with a liquid lubricant, and microporous PTFE hybrid flat membranes are prepared from the mixture through extrusion, calendaring, stretching and sintering. Then the microporous PTFE hybrid flat membranes are cut into membrane strips which wrap around supporting tubes, and finally the wrapped supporting tubes are sintered to obtain the hollow fiber membranes and the tubular membranes. The polyvinylidene fluoride resin added into the products of the invention has a melting point around 160 DEG C, fuses while sintered at a temperature between 250 and 340 DEG C, and can largely increase the hardness of the flat membranes after solidification, which facilitates slitting of the flat membranes. During the process of sintering after wrapping, the polyvinylidene fluoride resin contained in the flat membranes fuses again when sintered at a temperature between 260 and 340 DEG C, and thus can be used as overlapping parts between the wrapped flat membranes and as binders between the flat membranes and the microporous supporting tubes, so that the bonding strength is substantially improved.
Description
Technical field
The present invention relates to the preparation method of hollow-fibre membrane and tubular membrane, be specifically related to the method for the standby hollow-fibre membrane of a kind of pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane looping legal system and tubular membrane.
Background technology
Film separates and mainly comprises plate and frame, doughnut formula, rolling and four kinds of forms of tubular type with membrane module form, and the membrane material form that adopts is respectively Flat Membrane, hollow-fibre membrane, rolled film and tubular membrane.The characteristics such as the hollow-fibre membrane occupation of land is little, should not block up, easy to maintenance.
The characteristics such as microporous teflon membran has that porosity is high, aperture is adjustable, high-low temperature resistant, corrosion-resistant, anti-microbiological attack, have very important using value at the film separation field.Microporous teflon membran mainly comprises Flat Membrane and hollow-fibre membrane, and it is to adopt the decentralized polyflon, and this material can form the microstructure of " fibril-node " under shear action, and fibril and node can form micropore.The master operation preparations such as the Flat Membrane work flow is generally that raw material and lubricating oil are mixed, slaking, paste-extruded, calendering, degreasing, stretching, sintering typing, wherein stretch and can adopt unidirectional or biaxial tension., for the polytetrafluoroethylene film of processing porosity prosperity, mostly adopt the method for biaxial tension, i.e. first vertically rear horizontal method.Adopt the biaxial tension technology, but the aperture modification scope is large.The master operation preparations such as the polytetrafluoroethylhollow hollow fiber membrane work flow is generally that raw material and lubricating oil are mixed, slaking, paste-extruded, degreasing, stretching, sintering typing,, because the hollow-fibre membrane internal-and external diameter is less, be difficult to carry out cross directional stretch, be only generally longitudinal stretching, draw ratio is larger, and aperture is just larger, porosity larger (Zhang Huapeng, Zhu Hailin, Wang Feng, Guo Yuhai, the preparation of polytetrafluoroethylhollow hollow fiber membrane, membrane science and technology, 2013,1,17-21).So very difficult processing aperture is little, the large hollow-fibre membrane of while porosity.
Under this background, multinomial hollow-fibre membrane or tubular membrane looping technology take the polytetrafluoroethylene film as filter course appearred, supporting layer can be polytetrafluoroethylene (PTFE) or other materials.As, adopt terylene (PET) fiber braided tube as stay pipe in patent 201110217618, application of adhesive on the PET fiber braided tube; On the PET fiber braided tube, Flat Membrane adjacent during looping overlaps with the continuous looping of polytetrafluoroethylene film; Oven dry finally., by selecting Flat Membrane can accurately control the aperture of polytetrafluoroethylhollow hollow fiber membrane, effectively improve the porosity of polytetrafluoroethylhollow hollow fiber membrane, thereby promote the membrane flux of tunica fibrosa.In patent 200310124868.4,, by wrapped polytetrafluoroethylene film outside the polytetrafluoroethylhollow hollow fiber supporting layer, improve the performance of anti-blockage of polytetrafluoroethylhollow hollow fiber membrane.Patent 201210547439 with polytetrafluoroethylene (PTFE) not sintering or half sintered membrane be wrapped on stay pipe, then sintering, obtain wrapped type polytetrafluoroethylene (PTFE) ultra filtration tubular membrane.The patent 201120193277.2 expanded microporous polytetra fluoroethylene-EPTEE Flat Membrane looping of one deck pore diameter range 0.02-0.5 μ m, thickness 5-100 μ m at least is on the polytetrafluoroethylhollow hollow fiber of 0.5-2 μ m at pore diameter range, processing polytetrafluoroethylregenerated hollow-fibre membrane.Patent 200910225824.8 is by wrapped polytetrafluoroethylene (PTFE) film preparation polytetrafluoroethylene (PTFE) hollow membrane outside the braids such as polytetrafluoroethylene fibre, glass fibre, asbestos fibre.
Polytetrafluoroethylhollow hollow fiber membrane and tubular membrane mostly are used for field of waste water treatment, and application mode is general adopts interior the pressure or external pressure, but no matter adopts which kind of mode, and hollow-fibre membrane and tubular membrane must be born certain pressure.Although and the method for looping can precisely be controlled aperture, overlap between the Flat Membrane of looping, and Flat Membrane and the direct bonding of backing material must reach very high intensity.For the decentralized polytetrafluoroethylmaterial material, by controlling the sintering degree, and under certain temperature and pressure, can realize self-adhesion to a certain degree, be exactly to control lubricating oil content in polytetrafluoroethylmaterial material by sintering as patent 201110446377.6, realize the self-adhesion of material under hot pressing.
For polytetrafluoroethylene film looping technology, except adhesion problem, an another one difficult problem that faces is how the polytetrafluoroethylene film cuts into strip material.For making hollow-fibre membrane and tubular membrane reach a higher water flux, thickness that must the reduce Flat Membrane, the polytetrafluoroethylene film is very soft simultaneously, and cutting thin and soft polytetrafluoroethylene film is technical bottleneck.
Summary of the invention
In order to overcome the problem that exists in background technology, the object of the present invention is to provide the method for the standby hollow-fibre membrane of a kind of pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane looping legal system and tubular membrane, the method is that decentralized polyflon, polyvinylidene fluoride resin and fluid lubricant is mixed, through extruding, roll, the techniques such as stretching, sintering prepare pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane, cut into again belt type film, looping is on stay pipe, and last sintering forms.
The step of the technical solution used in the present invention is as follows:
(1) pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane: with the decentralized polyflon, polyvinylidene fluoride resin and fluid lubricant 1:0.02-0.08:0.2-0.3 by weight percentage are evenly mixed, at the temperature of 20 ~ 40 ℃ standing 96 ~ 144 hours, then at the temperature of 40 ~ 80 ℃ standing 10 ~ 16 hours, under 20 ~ 30 ℃, be pressed into cylindrical blank on harder, blank is extruded club by plunger piston extrusion machine at the temperature of 40 ~ 60 ℃, then be rolled into base band through calender under 40 ~ 60 ℃, described base band is carried out longitudinal stretching 1-6 in the baking oven of 180 ~ 300 ℃ doubly, carry out again 2-5 cross directional stretch doubly, finally at 250-340 ℃ of lower sintering, 10 ~ 30 seconds time, obtain aperture 0.03-0.2 micron, the pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane of thickness 5-50 micron,
(2) cut: the belt type film that described pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane is cut into width 5～9 mm wides;
(3) looping:, with described belt type film spiral looping 1-10 layer on porous tubular support, obtain fasciated tube;
(4) sintering: described fasciated tube, at 260-340 ℃ of lower sintering, time 20-80 second, is prepared hollow-fibre membrane and tubular membrane.
The degree of crystallinity of described decentralized polyflon is 98 ~ 99.9%, molecular weight is 2,000,000 ~ 10,000,000.Adopt commercially available prod, as hugeization group 188, the F106 of Daikin company.
Described fluid lubricant is atoleine, benzinum or kerosene.
Described porous tubular support is polytetrafluoroethylhollow hollow fiber membrane (as by patent 201010508798 processing), porous ceramic pipe, stainless steel wire woven tube or carbon fiber knit pipe.
Described polyvinylidene fluoride resin, fusing point are 160 ℃ of left and right.Adopt commercially available prod, as FR904, the FR921 of the Shanghai three rich new material of love limited companies.
Compare with background technology, the beneficial effect that the present invention has is:
(1) the present invention adds polyvinylidene fluoride resin in preparing pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane, its fusing point is 160 ℃ of left and right, sintering melting at the temperature of 250-340 ℃, solidify the hardness that can greatly increase Flat Membrane afterwards, and this is very beneficial for cutting of Flat Membrane.
(2) in the process of the present invention's sintering after looping, because contain polyvinylidene fluoride resin in Flat Membrane, can melting again under 260-340 ℃ of sintering, can be used as the binding agent of overlap between the Flat Membrane of looping and Flat Membrane and porous tubular support, greatly strengthen adhesion strength.
The specific embodiment
Embodiment 1:
(1) pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane: with 188 decentralized polyflons of hugeization group, the FR904 polyvinylidene fluoride resin of Shanghai Sanaifu New Material Co., Ltd and atoleine 1:0.02:0.3 by weight percentage are evenly mixed, at the temperature of 20 ℃ standing 96 hours, then at the temperature of 40 ℃ standing 10 hours, under 20 ℃, be pressed into cylindrical blank on harder, blank is extruded club by plunger piston extrusion machine at the temperature of 60 ℃, then be rolled into base band through calender under 40 ℃, described base band is carried out 1 times of longitudinal stretching in the baking oven of 180 ℃, carry out again the cross directional stretch of 2 times, finally at 250 ℃ of lower sintering, 30 seconds time, obtain 0.03 micron, aperture, the pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane that thickness is 50 microns,
(2) cut: the belt type film that described pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane is cut into width 5 mm wides;
(3) looping:, with described belt type film 1 layer of spiral looping on the polytetrafluoroethylhollow hollow fiber membrane by patent 201010508798 processing, obtain fasciated tube;
(4) sintering: described fasciated tube, at 260 ℃ of lower sintering, 80 seconds time, is prepared hollow-fibre membrane.
Embodiment 2:
(1) pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane: with 188 decentralized polyflons of hugeization group, the FR921 polyvinylidene fluoride resin of Shanghai Sanaifu New Material Co., Ltd and kerosene 1:0.08:0.2 by weight percentage are evenly mixed, at the temperature of 40 ℃ standing 144 hours, then at the temperature of 80 ℃ standing 16 hours, under 30 ℃, be pressed into cylindrical blank on harder, blank is extruded club by plunger piston extrusion machine at the temperature of 40 ℃, then be rolled into base band through calender under 60 ℃, described base band is carried out 6 times of longitudinal stretchings in the baking oven of 300 ℃, carry out again the cross directional stretch of 5 times, finally at 340 ℃ of lower sintering, 10 seconds time, obtain 0.2 micron, aperture, the pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane that thickness is 5 microns,
(2) cut: the belt type film that described pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane is cut into width 9 mm wides;
(3) looping:, with described belt type film 10 layers of spiral loopings on porous ceramic pipe, obtain fasciated tube;
(4) sintering: described fasciated tube, at 340 ℃ of lower sintering, 20 seconds time, is prepared tubular membrane.
Embodiment 3:
(1) pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane: with the F106 decentralized polyflon of Daikin company, the FR921 polyvinylidene fluoride resin of Shanghai Sanaifu New Material Co., Ltd and benzinum 1:0.05:0.25 by weight percentage are evenly mixed, at the temperature of 30 ℃ standing 100 hours, then at the temperature of 60 ℃ standing 15 hours, under 25 ℃, be pressed into cylindrical blank on harder, blank is extruded club by plunger piston extrusion machine at the temperature of 50 ℃, then be rolled into base band through calender under 50 ℃, described base band is carried out 3 times of longitudinal stretchings in the baking oven of 200 ℃, carry out again the cross directional stretch of 3 times, finally at 280 ℃ of lower sintering, 20 seconds time, obtain 0.15 micron, aperture, the pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane that thickness is 20 microns,
(2) cut: the belt type film that described pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane is cut into width 7 mm wides;
(3) looping:, with described belt type film 5 layers of spiral loopings on the stainless steel wire woven tube, obtain fasciated tube;
(4) sintering: described fasciated tube, at 280 ℃ of lower sintering, 60 seconds time, is prepared tubular membrane.
Embodiment 4:
(1) pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane: with the F106 decentralized polyflon of Daikin company, the FR921 polyvinylidene fluoride resin of Shanghai Sanaifu New Material Co., Ltd and benzinum 1:0.06:0.25 by weight percentage are evenly mixed, at the temperature of 30 ℃ standing 100 hours, then at the temperature of 60 ℃ standing 15 hours, under 25 ℃, be pressed into cylindrical blank on harder, blank is extruded club by plunger piston extrusion machine at the temperature of 50 ℃, then be rolled into base band through calender under 50 ℃, described base band is carried out 4 times of longitudinal stretchings in the baking oven of 200 ℃, carry out again the cross directional stretch of 4 times, finally at 280 ℃ of lower sintering, 20 seconds time, obtain 0.18 micron, aperture, the pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane that thickness is 18 microns,
(2) cut: the belt type film that described pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane is cut into width 8 mm wides;
(3) looping:, with described belt type film 6 layers of spiral loopings on the carbon fiber knit pipe, obtain fasciated tube;
(4) sintering: described fasciated tube, at 280 ℃ of lower sintering, 60 seconds time, is prepared tubular membrane.
Claims (4)
1. the method for the standby hollow-fibre membrane of a pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane looping legal system and tubular membrane, is characterized in that, the step of the method is as follows:
(1) pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane: with the decentralized polyflon, polyvinylidene fluoride resin and fluid lubricant 1:0.02-0.08:0.2-0.3 by weight percentage are evenly mixed, at the temperature of 20 ~ 40 ℃ standing 96 ~ 144 hours, then at the temperature of 40 ~ 80 ℃ standing 10 ~ 16 hours, under 20 ~ 30 ℃, be pressed into cylindrical blank on harder, blank is extruded club by plunger piston extrusion machine at the temperature of 40 ~ 60 ℃, then be rolled into base band through calender under 40 ~ 60 ℃, described base band is carried out longitudinal stretching 1-6 in the baking oven of 180 ~ 300 ℃ doubly, carry out again 2-5 cross directional stretch doubly, finally at 250-340 ℃ of lower sintering, 10 ~ 30 seconds time, obtain aperture 0.03-0.2 micron, the pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane of thickness 5-50 micron,
(2) cut: the belt type film that described pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane is cut into width 5～9 mm wides;
(3) looping:, with described belt type film spiral looping 1-10 layer on porous tubular support, obtain fasciated tube;
(4) sintering: described fasciated tube, at 260-340 ℃ of lower sintering, time 20-80 second, is prepared hollow-fibre membrane and tubular membrane.
2. the method for the standby hollow-fibre membrane of a kind of pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane looping legal system according to claim 1 and tubular membrane is characterized in that: the degree of crystallinity of described decentralized polyflon is 98 ~ 99.9%, molecular weight is 2,000,000 ~ 10,000,000.
3. a kind of pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane looping legal system according to claim 1 is for the method for hollow-fibre membrane and tubular membrane, and it is characterized in that: described fluid lubricant is atoleine, benzinum or kerosene.
4. a kind of pore type polytetrafluoroethylene (PTFE) hydridization Flat Membrane looping legal system according to claim 1 is for the method for hollow-fibre membrane and tubular membrane, and it is characterized in that: described porous tubular support is polytetrafluoroethylhollow hollow fiber membrane, porous ceramic pipe, stainless steel wire woven tube or carbon fiber knit pipe.
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103736399A (en) * | 2014-01-20 | 2014-04-23 | 天津工业大学 | Full-fluorine polymer hollow fibrous membrane and preparation method thereof |
| CN103949165A (en) * | 2014-03-27 | 2014-07-30 | 宁波净源膜科技有限公司 | Polytetrafluoroethylene heterogeneous phase hollow fiber membrane preparation method |
| CN104894675A (en) * | 2015-06-25 | 2015-09-09 | 常州万容新材料科技有限公司 | Manufacturing technology of high-strength low-elongation polytetrafluoroethylene filaments |
| CN105013345A (en) * | 2014-04-22 | 2015-11-04 | 成都百途医药科技有限公司 | Preparation method of super-hydrophobic polytetrafluoroethylene film |
| CN105013347A (en) * | 2014-04-22 | 2015-11-04 | 成都百途医药科技有限公司 | Preparation method of super-hydrophobic polytetrafluoroethylene film |
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Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103736399A (en) * | 2014-01-20 | 2014-04-23 | 天津工业大学 | Full-fluorine polymer hollow fibrous membrane and preparation method thereof |
| CN103949165A (en) * | 2014-03-27 | 2014-07-30 | 宁波净源膜科技有限公司 | Polytetrafluoroethylene heterogeneous phase hollow fiber membrane preparation method |
| CN105013345A (en) * | 2014-04-22 | 2015-11-04 | 成都百途医药科技有限公司 | Preparation method of super-hydrophobic polytetrafluoroethylene film |
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| CN104894675A (en) * | 2015-06-25 | 2015-09-09 | 常州万容新材料科技有限公司 | Manufacturing technology of high-strength low-elongation polytetrafluoroethylene filaments |
| CN105664733A (en) * | 2016-01-21 | 2016-06-15 | 巨化集团技术中心 | Preparation method of perfluoro hollow fiber composite film |
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| CN109529639A (en) * | 2018-11-05 | 2019-03-29 | 宁波水艺膜科技发展有限公司 | The preparation method of high bond strength polytetrafluoroethylhollow hollow fiber membrane |
| CN109529639B (en) * | 2018-11-05 | 2021-08-17 | 宁波水艺膜科技发展有限公司 | Preparation method of polytetrafluoroethylene hollow fiber membrane with high bonding strength |
| CN111192995A (en) * | 2018-11-15 | 2020-05-22 | 微宏动力系统（湖州）有限公司 | High-cohesiveness battery diaphragm, preparation method thereof and lithium ion battery |
| CN109621737A (en) * | 2019-01-07 | 2019-04-16 | 浙江净膜环保有限责任公司 | The preparation method of the PTFE/PFA composite membrane of high porosity |
| CN111152533A (en) * | 2020-01-03 | 2020-05-15 | 青岛大学 | Multifunctional expanded polytetrafluoroethylene plate and lamination composite preparation process thereof |
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| CN113878835A (en) * | 2021-12-08 | 2022-01-04 | 国家电投集团氢能科技发展有限公司 | Polytetrafluoroethylene/carbon fiber composite release film and preparation method and application thereof |
| CN113878835B (en) * | 2021-12-08 | 2022-03-08 | 国家电投集团氢能科技发展有限公司 | Polytetrafluoroethylene/carbon fiber composite release film and preparation method and application thereof |
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