CN101007242A - Preparation method of expanding microporous poly tetrafluoroethylene - Google Patents
Preparation method of expanding microporous poly tetrafluoroethylene Download PDFInfo
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Abstract
An expanded micropore polytetrafluoroethylene film (it is named ePTFE film briefly) Preparation is an improved method of the existing polytetrafluoroethylene film preparation. It includes mixing materials, striking adobe, squeezing, pulling longitudinally and pulling horizontally, it is characterized by: using the mold head of flat finish mold in squeezing procedure; adding glazing procedure between the squeezing procedure and pulling longitudinally procedure. The ePTFE film prepared by the technology can balance two important physics properties of permeability and stretching splitting strong force of ePTFE film and gain the ePTFE film with high permeability, high stretching splitting strong force, high uniformity and good appearance. The invention can be uses for produce mass ePTFE film with stabilizing appearance and property and improve the products property of the ePTFE film effectively.
Description
Technical field
The preparation method of expanding microporous poly tetrafluoroethylene (hereinafter to be referred as the ePTFE film) is the improvement to existing ePTFE membrane preparation method.
Background technology
Polytetrafluoroethylene (PTFE) has good high temperature performance, outstanding chemical stability, and excellent dielectric properties and hydrophobicity.Adopting polytetrafluoroethylene (PTFE) is the ePTFE film of feedstock production; be a kind of filtration of function admirable and the membrane material of separate fine particle; ash-laden gas among the industries such as its extensive use cement, metallurgy, electric power filters, to satisfy the requirement of industry environmental protection and cleaner production.
The ePTFE film has the microcosmic network structure of " microfibre one node ".Air penetrability is one of its important physical parameter, and it has determined the complexity of ash-laden gas gas by medium, has showed the transmission performance of medium to gas.The powerful F of tension failure is its another important physical parameter.Carry out the test of film strength P and the powerful F of tension failure with reference to JC/T768 tension failure strength test standard, wherein the pass of the powerful F of intensity P and tension failure is F=P * S, S is the sectional area of sample, under the certain condition of specimen width, sectional area S is directly proportional with the thickness of sample, thereby under the certain condition of film strength P, the powerful F of tension failure is directly proportional with the thickness of film.The tension failure brute force of film is high more, and the service life of film is also just long more.But as filtering material, the ePTFE film is too thick, and air penetrability can reduce, and strainability can variation.How to make existing high air penetrability, the ePTFE film that the powerful mechanical property of high tension failure is arranged again is to need a technical barrier exploring at present both at home and abroad in the ePTFE film production process.
Produce at present that the ePTFE film is taked batch mixing, striking adobe, extrudes, rolled, vertically draws, horizontal six procedures that draw, specifically referring to Fig. 1.
In the extruding zone operation, cylinder blank enters the preformation die cavity of pushing the cylinder entrance point and obtains compacting, is full of the material chamber of pushing the cylinder middle part more gradually, enters the shaping mould draught animals mould of pushing the cylinder port of export at last.By dwindling greatly, the minification of blank sectional area just is called compression ratio (Reduction Ratio), represents with RR at this stage blank cross-sectional area.The computing formula of compression ratio is as follows:
S wherein
1The preformed die cavity cross-sectional area of cylinder entrance point is pushed in representative; s
2The shaping mould draught animals mould cross-sectional area of the cylinder port of export is pushed in representative.
In the preparation process of ePTFE film, compression ratio is a very important parameter, and it and ePTFE film product quality are closely bound up.Usually the increase of compression ratio helps improving film strength, so all adopt higher compression recently to improve film strength in the production extruding zone operation of present ePTFE film.Simultaneously, in existing production method, generally adopt the die head of circular port mould, owing to extrude the influence of rod height, the resistance when it enters calender is bigger, and simultaneously, it is poor to extrude excellent stretching capability when using the circular port mould.So, in existing production process, extruding operation after, ensuing operation be the calendering.
The mode of production by " extruding earlier; the back calendering ", in calender line, when extruding band through stack, material is simultaneously to middle and two side flow, and the third side often greater than both sides, can uneven problem occur flowing to material movement speed in the both sides and the centre of calendering band, like this, very easily cause the calendering band of tearing or make of calendering band to produce the shirt rim; From microcosmic angle, very easily make the polytetrafluoroethylene (PTFE) material produce pro-fibrotic, thereby on film, form a large amount of lines, influence the cancellated uniformity of microcosmic of " microfibre-node ", influence the presentation quality of ePTFE film.
Summary of the invention
Problem at above-mentioned existing ePTFE membrane preparation method existence, the present invention proposes a kind of preparation method of new ePTFE film, it can take into account the air penetrability of ePTFE film and powerful these two important physical properties of tension failure simultaneously, and improves the microcosmic network structure uniformity of inherence " microfibre-node " of film and the presentation quality of ePTFE film greatly.
Technical solution of the present invention is as follows: it comprises batch mixing, striking adobe, extrudes, vertically draw, the horizontal operation of drawing, and it is characterized in that: the die head that adopts flat pattern mouth mould in extruding operation; Extruding and vertical drawing increased calendering operation together between the operation.Process flow diagram is referring to accompanying drawing 2.
Concrete processing step of this preparation method and condition are as follows:
(1) batch mixing: polyflon and the auxiliary agent raw material chosen are fully stirred;
(2) striking adobe: will be through the even mixed raw material of last process, under 40 ℃ of temperature, fully soak into after inserting baking oven, make the column base substrate by pre-shaping device;
(3) extrude: adopt the die head flat-die of pancake mouth mould to extrude, extrude load pressure and be controlled at 3～4Mp, extruded velocity is 1～5m/min, makes the column base substrate be transformed into the flat belt-like sheet material;
(4) calendering: with the flat belt-like sheet material of extruding is that hauling speed is 1～5m/min under the pressure roller effect of 20～30Kg/cm at linear pressure, is made into the broadband that thickness is 150～500 μ m;
(5) vertical drawing: with the broadband that last process makes, under 100 ℃～250 ℃ temperature, vertical drawing is prepared into the vertical base band of drawing;
(6) horizontal drawing: the vertical base band of drawing with last process makes at 50 ℃～350 ℃ following cross directional stretch, at 340 ℃ of-370 ℃ of curing moldings, makes the ePTFE film.
The ratio of width to height of the die head of used pancake mouth mould is 70～250: 1 in extruding operation, and the compression ratio range of extruding in the operation is 10～50.
Die head is to produce the shaping jig of extruding band, and it plays important effect to the aspects such as air penetrability, thickness, uniformity and outward appearance of product.Abandon existing circular port mould, select for use the big and port of export of the ratio of width to height to be the die head of pancake mouth mould, provide a kind of and obtained wide and the new tool flat pattern base band.
By the compression ratio formula as can be known, compression ratio is related closely with the design of die head mouth mould.Pushing cylinder preformed die cavity cross-sectional area (s
1) under the constant situation, the sectional area (s of die head mouth mould
2) determined the size of compression ratio.Increase the sectional area (s of die head mouth mould
2), reducing compression ratio, the packing of blank reduces, and makes the air penetrability of telolemma to be improved.Facts have proved the tension failure brute force that adopts the ratio of width to height that the present invention selects for use and compression ratio range can on the basis of the gas permeability that satisfies the ePTFE film, improve film, increase the service life by the thickness of suitable increase film.
After the process program that material is being extruded the flat pattern mouth mould die head selected for use by the present invention in the operation and low compression ratio was extruded, if still use existing calendering procedure, its result further amplified the open defect of extruding band.Because compare with the process program of circular port mould and high compression ratio, consequently blank density reduces, calendering procedure is to extrude band exhibition length, broadening, ironed process, the mobile displacement of material is very big in the calendering band, cause the inhomogeneous of film appearance inevitably, this situation is more outstanding under the low density situation of blank.
In the present invention, extruding after the operation is the calendering operation.The calendering operation is used uniform transverse pressure to act on to extrude exactly and is with, and has improved because of the excessive harmful effect that uniformity is brought of blank shape conversion.After the calendering operation, strengthened the interparticle uniformity of material, i.e. cancellated uniformity of the microcosmic of " microfibre-node " and the fineness of extruding belt surface.Fig. 3 and Fig. 4 are respectively high resolution scanning electron microscope (SEM) photos of the ePTFE film of preparation before and after the process modification.
By test, we find, adopt process of the present invention, under identical compression ratio, identical thickness, select for use the ratio of width to height of pancake mouth mould die head bigger, and the presentation quality of its film better.
From table 1 we as can be seen, adopt process of the present invention, select the die head of the pancake mouth mould of identical the ratio of width to height for use, under the condition of different compression ratios, the performance variation of the ePTFE film that preparation thickness is suitable, compression ratio is dropped to 10 from 50, compression ratio reduces by 80%, and its air penetrability improves 143%, and the warp-wise intensity of film reduces by 23.4%, latitudinal strength reduces by 19.5%, and the percentage of the raising of its air penetrability is much higher than the percentage that intensity reduces.
We can find again from table 2, adopt process of the present invention, select the die head of the pancake mouth mould of identical the ratio of width to height for use, under the condition of identical compression ratio, the performance variation of the ePTFE film of preparation different-thickness, the thickness of film is brought up to 40.1 μ m from 15.8 μ m, the thickness of film improves 154%, its air penetrability reduces by 26.3%, intensity is suitable substantially, but its warp direction stretching ultimate strength improves 169%, and broadwise tension failure is powerful to improve 197%, and the percentage that its air penetrability reduces is significantly less than the powerful percentage that improves of tension failure.
In sum, adopt process of the present invention, select the die head of the pancake mouth mould of suitable the ratio of width to height for use, reduce compression ratio and the suitable technical scheme that improves thickness, can take into account powerful two physical properties of tension failure of the air penetrability and the film of raising film, can obtain to have high air penetrability simultaneously, high tension failure brute force, uniformity height, ePTFE film that outward appearance is good, its every performance is referring to table 3.The present invention can be used for the ePTFE film of continuous batch production outward appearance and stable performance, improves the properties of product of ePTFE film effectively.
Description of drawings
Fig. 1 is former process flow diagram
Fig. 2 is a process flow diagram of the present invention
Fig. 3 be former explained hereafter the ePTFE film the high resolution scanning electron microscope photo
Fig. 4 for the ePTFE film of explained hereafter of the present invention the high resolution scanning electron microscope photo
The specific embodiment
Embodiment 1:
Used in the present embodiment polyflon raw material is that commercially available HMW (molecular weight 8,000,000) decentralized polyflon, auxiliary agent are that arene isoparaffin and aviation kerosine are main mixture.Operate according to the following steps:
(1) batch mixing:, in agitator, fully stir with high molecular weight polytetrafluoroethyldispersions resin and auxiliary agent ratio with 100: 30;
(2) striking adobe: will be through the even mixed raw material of last process, insert baking oven after (under 40 ℃ of temperature) fully soak into 12h, make the column base substrate of diameter 104mm by pre-shaping device;
(3) extrude: adopting the ratio of width to height is that the die head flat-die of 70: 1 pancake mouth mould is extruded, and compression ratio is 10, and extruded velocity is 1m/min, makes the column base substrate be transformed into the sheet material of flat pattern, the wide 244mm of sheet material, and thick 3.48mm extrudes load pressure and is controlled at 3Mpa;
(4) calendering: with the flat belt-like sheet material of extruding is that hauling speed is 1m/min under the pressure roller effect of 20Kg/cm at linear pressure, is made into the broadband that thickness is 400 μ m;
(5) vertical drawing: the equipment longitudinal stretching under 200 ℃ high temperature, is drawn by vertical in above broadband, be prepared into the vertical base band of drawing;
(6) horizontal drawing: will indulge draw base band under 300 ℃ by the horizontal equipment cross directional stretch that draws, at 350 ℃ of curing moldings, make fabric width 2m, thickness is the ePTFE film of 21.3 μ m.
Embodiment 2:
Identical with embodiment 1 step, its technological parameter is compared with embodiment 1, and all the other are all identical except that following difference.Difference is that selected compression ratio is 30 in the extrusion step, and the wide 200mm of extrusion sheet, thick 1.4mm, prepared thickness are 22.5 μ m.
Embodiment 3:
Identical with embodiment 1 step, its technological parameter is compared with embodiment 1, and all the other are all identical except that following difference.Difference is that the column base substrate diameter that pre-shaping device is made is 60mm, and the wide 200mm of extrusion sheet, thick 1.4mm, prepared thickness are 21.2 μ m.
Embodiment 4:
Identical with embodiment 1 step, its technological parameter is compared with embodiment 1, and all the other are all identical except that following difference.Difference is that selected compression ratio is 50 in the extrusion step, and the column base substrate diameter that pre-shaping device is made is 134mm, and the wide 200mm of extrusion sheet, thick 1.4mm, prepared thickness are 21.9 μ m.
Embodiment 5:
Identical with embodiment 1 step, its technological parameter is compared with embodiment 1, and all the other are all identical except that following difference.Difference is that selected compression ratio is 30 in the extrusion step, and the wide 200mm of extrusion sheet, thick 1.4mm, prepared thickness are 15.8 μ m.
Embodiment 6:
Identical with embodiment 1 step, its technological parameter is compared with embodiment 1, and all the other are all identical except that following difference.Difference is that selected compression ratio is 30 in the extrusion step, and the wide 200mm of extrusion sheet, thick 1.4mm, prepared thickness are 18.1 μ m.
Embodiment 7:
Identical with embodiment 1 step, its technological parameter is compared with embodiment 1, and all the other are all identical except that following difference.Difference is that selected compression ratio is 30 in the extrusion step, and the wide 200mm of extrusion sheet, thick 1.4mm, prepared thickness are 31.6 μ m.
Embodiment 8:
Identical with embodiment 1 step, its technological parameter is compared with embodiment 1, and all the other are all identical except that following difference.Difference is that selected compression ratio is 30 in the extrusion step, and the wide 200mm of extrusion sheet, thick 1.4mm, prepared thickness are 40.1 μ m.
Embodiment 9:
Identical with embodiment 1 step, its technological parameter is compared with embodiment 1, and all the other are all identical except that following difference.Difference from Example 1 is that the die head flat-die of 250: 1 pancake mouth mould is extruded for adopting the ratio of width to height, and selected compression ratio is 50 in the extrusion step, and the column base substrate diameter that pre-shaping device is made is 126mm, the wide 250mm of extrusion sheet, thick 1mm.
Comparative example:
Table 3 is the film of the present invention's preparation and the film properties comparison of existing method preparation.Wherein comparative example is the production method of prior art.Adopt the extrusion molding of Φ 12mm circle die head, compression ratio 75, preparation ePTFE film.The concrete preparation process of comparative example is as follows:
(1) batch mixing:, in agitator, fully stir with high molecular weight polytetrafluoroethyldispersions resin and auxiliary agent ratio with 100: 30;
(2) striking adobe: will be through the even mixed raw material of last process, insert baking oven after (under 40 ℃ of temperature) fully soak into 12h, make the column base substrate of diameter 104mm by pre-shaping device;
(3) extrude: adopting compression ratio is the die head extrusion molding of 75 circular port mould, extrudes the pole of diameter 12mm, extrudes load pressure and is controlled at 3Mpa;
(4) calendering: the pole extruded stock is rolled the broadband of making the about 400 μ m of thickness through stack;
(5) vertical drawing: the equipment longitudinal stretching under 200 ℃ high temperature, is drawn by vertical in above broadband, be prepared into the vertical base band of drawing;
(6) horizontal drawing: will indulge draw base band under 300 ℃ by the horizontal equipment cross directional stretch that draws, at 350 ℃ of curing moldings, make the ePTFE film of fabric width 1.2m.
Table 1 prepares the variation of the performance of ePTFE film with compression ratio with the pancake mouth mould die head of the ratio of width to height
| Parameter | Performance | |||
| Embodiment 2 | Embodiment 3 | |
||
| Compression ratio | 30 | 10 | 50 | |
| Porosity (%) | 90.7 | 92.5 | 82.9 | |
| Air penetrability (cm/s) | 11.9 | 15.8 | 6.51 | |
| Thickness (μ m) | 22.5 | 21.2 | 21.9 | |
| The powerful F (N/25mm) of tension failure | Warp-wise | 23.4 | 19.6 | 26.5 |
| Broadwise | 4.47 | 3.75 | 4.82 | |
| Intensity P (MPa) | Warp-wise | 41.6 | 37.3 | 48.7 |
| Broadwise | 7.92 | 7.12 | 8.85 | |
| The film outward appearance | Well | Well | Well | |
| Compression ratio reduces (%) | 40 | 80 | / | |
| Air penetrability improves (%) | 82.8 | 143 | / | |
| The powerful F of tension failure reduces (%) | Warp-wise | 11.7 | 26.0 | / |
| Broadwise | 7.3 | 22.1 | / | |
| Intensity P reduces (%) | Warp-wise | 14.6 | 23.4 | / |
| Broadwise | 10.5 | 19.5 | / | |
Table 2 with the ratio of width to height pancake mouth mould die head with the variation of the performance of ePTFE film under the compression ratio with thickness
| |
Embodiment 6 | Embodiment 2 | Embodiment 7 | |
||
| Compression ratio | 30 | 30 | 30 | 30 | 30 | |
| Thickness (μ m) | 15.8 | 18.1 | 22.5 | 31.6 | 40.1 | |
| Porosity (%) | 91.0 | 88.7 | 90.7 | 89.1 | 91.1 | |
| Air penetrability (cm/s) | 13.3 | 12.7 | 11.9 | 10.2 | 9.8 | |
| The powerful F (N/25mm) of tension failure | Warp-wise | 15.5 | 17.4 | 23.4 | 31.8 | 41.7 |
| Broadwise | 2.83 | 3.18 | 4.47 | 6.50 | 8.42 | |
| Intensity P (MPa) | Warp-wise | 39.4 | 38.5 | 41.6 | 40.3 | 42.1 |
| Broadwise | 7.43 | 7.01 | 7.92 | 8.23 | 8.45 | |
| Thickness improves (%) | / | 12.7 | 42.4 | 100 | 154 | |
| Air penetrability reduces (%) | / | 4.5 | 10.5 | 23.3 | 26.3 | |
| The powerful F of tension failure improves (%) | Warp-wise | / | 12.2 | 50.9 | 105 | 169 |
| Broadwise | / | 12.3 | 57.9 | 129 | 197 | |
Preparation ePTFE film properties relatively under table 3 technology of the present invention and the prior art condition
| Parameter | Performance | ||
| Comparative example | Embodiment 2 | ||
| Compression ratio | 75 | 30 | |
| Porosity mean value (%) | 72.73 | 90.7 | |
| Air penetrability (cm/s) | 2.96 | 11.9 | |
| Thickness (μ m) | 9.13 | 22.5 | |
| The powerful F (N/25mm) of tension failure | Warp-wise | 12.4 | 23.4 |
| Broadwise | 2.32 | 4.47 | |
| Intensity P (MPa) | Warp-wise | 54.6 | 41.6 |
| Broadwise | 9.92 | 7.92 | |
| The film outward appearance | Can not draw away in the middle of the film, decorative pattern is many, and time has and breaks | Well | |
| Compression ratio reduces (%) | / | 96 | |
| Thickness improves (%) | / | 146 | |
| Air penetrability improves (%) | / | 302 | |
| The powerful F of tension failure improves (%) | Warp-wise | / | 88.7 |
| Broadwise | / | 86.2 | |
| Intensity P reduces (%) | Warp-wise | / | 23.8 |
| Broadwise | / | 20.2 | |
Claims (3)
1, the preparation method of expanding microporous poly tetrafluoroethylene, it comprises: batch mixing, striking adobe, extrude, vertical draw, the horizontal operation of drawing, it is characterized in that: the die head that in extruding operation, adopts flat pattern mouth mould; Extruding and vertical drawing increased calendering operation together between the operation, concrete processing step of this preparation method and condition are as follows:
(1) batch mixing: polyflon and the auxiliary agent raw material chosen are fully stirred;
(2) striking adobe: will be through the even mixed raw material of last process, under 40 ℃ of temperature, fully soak into after inserting baking oven, make the column base substrate by pre-shaping device;
(3) extrude: adopt the die head flat-die of pancake mouth mould to extrude, extrude load pressure and be controlled at 3～4Mpa, extruded velocity is 1～5m/min, makes the column base substrate be transformed into the flat belt-like sheet material;
(4) calendering: with the flat belt-like sheet material of extruding is that hauling speed is 1～5m/min under the pressure roller effect of 20～30Kg/cm at linear pressure, is made into the broadband that thickness is 150～500 μ m;
(5) vertical drawing: with the broadband that last process makes, under 100 ℃～250 ℃ temperature, vertical drawing is prepared into the vertical base band of drawing;
(6) horizontal drawing: the vertical base band of drawing with last process makes at 50 ℃～350 ℃ following cross directional stretch, at 340 ℃ of-370 ℃ of curing moldings, makes the ePTFE film.
2, the preparation method of expanding microporous poly tetrafluoroethylene according to claim 1 is characterized in that: the ratio of width to height of the die head of used pancake mouth mould is 70～250: 1 in extruding operation.
3, the preparation method of expanding microporous poly tetrafluoroethylene according to claim 1 is characterized in that: the compression ratio range of extruding in the operation is 10～50.
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| CN101879419A (en) * | 2010-07-06 | 2010-11-10 | 中材科技股份有限公司 | Multilayer polytetrafluoroethylene membrane as well as preparation method and device thereof |
| CN102248715A (en) * | 2011-05-10 | 2011-11-23 | 常州市泛亚微透科技有限公司 | Modified material film of micropore film composite nonwoven fabric for waterproof dustproof acoustically transparent expanded polytetrafluoroethylene (PTFE) and preparation method thereof |
| CN102649594A (en) * | 2012-02-28 | 2012-08-29 | 东营华泰化工集团有限公司 | Nitrate removal technology by membrane method |
| CN102658038A (en) * | 2012-04-10 | 2012-09-12 | 杭州洁弗膜技术有限公司 | Preparation method of sub-high efficiency polytetrafluoroethylene (PTFE) micro-porous film and film lamination material |
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| CN104015372A (en) * | 2014-01-09 | 2014-09-03 | 宁波氟纳斯氟材科技有限公司 | Production process and device of expanded polytetrafluoroethylene board |
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| CN104415672A (en) * | 2013-08-21 | 2015-03-18 | 黄天宇 | High-filtering-precision polytetrafluoroethylene microporous membrane preparing method |
| CN106738780A (en) * | 2016-12-13 | 2017-05-31 | 上海康宁医疗用品有限公司 | A kind of e PTFE plunger expressing techniques |
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| CN102248715A (en) * | 2011-05-10 | 2011-11-23 | 常州市泛亚微透科技有限公司 | Modified material film of micropore film composite nonwoven fabric for waterproof dustproof acoustically transparent expanded polytetrafluoroethylene (PTFE) and preparation method thereof |
| CN102248715B (en) * | 2011-05-10 | 2013-10-02 | 常州市泛亚微透科技有限公司 | Modified material film of micropore film composite nonwoven fabric for waterproof dustproof acoustically transparent expanded polytetrafluoroethylene (PTFE) and preparation method thereof |
| CN102649594A (en) * | 2012-02-28 | 2012-08-29 | 东营华泰化工集团有限公司 | Nitrate removal technology by membrane method |
| CN102658038A (en) * | 2012-04-10 | 2012-09-12 | 杭州洁弗膜技术有限公司 | Preparation method of sub-high efficiency polytetrafluoroethylene (PTFE) micro-porous film and film lamination material |
| CN103272497A (en) * | 2013-04-22 | 2013-09-04 | 浙江国泰密封材料股份有限公司 | Preparation method for multifunctional PTFE composite film |
| CN103272497B (en) * | 2013-04-22 | 2015-11-18 | 浙江国泰密封材料股份有限公司 | A kind of preparation method of multifunctional PTFE composite film |
| CN104415672A (en) * | 2013-08-21 | 2015-03-18 | 黄天宇 | High-filtering-precision polytetrafluoroethylene microporous membrane preparing method |
| CN104015372A (en) * | 2014-01-09 | 2014-09-03 | 宁波氟纳斯氟材科技有限公司 | Production process and device of expanded polytetrafluoroethylene board |
| CN104191680A (en) * | 2014-09-03 | 2014-12-10 | 青岛志腾工贸有限公司 | Cover film material applied to solid waste composting fermentation process |
| CN106738780A (en) * | 2016-12-13 | 2017-05-31 | 上海康宁医疗用品有限公司 | A kind of e PTFE plunger expressing techniques |
| CN106738780B (en) * | 2016-12-13 | 2019-02-22 | 上海康宁医疗用品有限公司 | A kind of e-PTFE plunger extrusion process |
| CN107962789A (en) * | 2017-12-11 | 2018-04-27 | 项朝卫 | A kind of continuous producing apparatus of high-performance ePTFE microporous barriers |
| CN108568220A (en) * | 2018-04-26 | 2018-09-25 | 杭州科百特过滤器材有限公司 | The preparation method of polytetrafluorethylenano nano filter membrane |
| 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 |
| 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 |
| CN112108008A (en) * | 2020-10-13 | 2020-12-22 | 上海希沃环境科技有限公司 | Polytetrafluoroethylene biaxially-oriented film and preparation method and application thereof |
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