CN1621139A - Method for preparing for polyvinylidene fluoride hollow fiber microporous film by melt spinning-pull stretching method - Google Patents
Method for preparing for polyvinylidene fluoride hollow fiber microporous film by melt spinning-pull stretching method Download PDFInfo
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- CN1621139A CN1621139A CN 200410067007 CN200410067007A CN1621139A CN 1621139 A CN1621139 A CN 1621139A CN 200410067007 CN200410067007 CN 200410067007 CN 200410067007 A CN200410067007 A CN 200410067007A CN 1621139 A CN1621139 A CN 1621139A
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 16
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 16
- 239000012510 hollow fiber Substances 0.000 title claims description 16
- 239000000835 fiber Substances 0.000 claims abstract description 49
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 230000004927 fusion Effects 0.000 claims description 3
- 238000007493 shaping process Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 238000009987 spinning Methods 0.000 abstract description 30
- 238000002360 preparation method Methods 0.000 abstract description 15
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 7
- 238000002166 wet spinning Methods 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000000578 dry spinning Methods 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 235000012489 doughnuts Nutrition 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 11
- 238000002074 melt spinning Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000012982 microporous membrane Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 238000007664 blowing Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 238000010276 construction Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 238000002145 thermally induced phase separation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000009998 heat setting Methods 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000409 membrane extraction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention is melting spinning and stretching process of preparing hollow polyvinylidene fluoride fiber film. The present invention features that hollow polyvinylidene fluoride fiber film is prepared through melting spinning and stretching process, which is superior to available wet spinning process and dry/wet spinning process in that there are no solvent and additive needed, no environmental pollution and simple preparation process. The hollow polyvinylidene fluoride fiber film features break strength of 100-150 MPa, elongation at breaking of 150-400 %, porosity of 25-65 %, average pore size of 0.01-0.1 micron, air penetrability of 0.000001-0.01 cu cm/sq cm.s.cmHg, film inner diameter of 150-400 micron and wall thickness of 30-60 micron.
Description
Technical field
The present invention relates to prepare the method for Kynoar hollow-fibre membrane with melt-spun-pulling method.
Background technology
Kynoar (PVDF) is a kind of membrane material of excellent performance, has been widely used in every field such as film separation and chemical industry, environmental protection, medical treatment.
About the Kynoar hollow-fibre membrane, the main method of preparation is to prepare by the solution phase inversion at present, in Chinese patent Nos.95117497 and 98103153, describe in detail with wet method and do-wet spinning prepares the technology of Kynoar hollow-fibre membrane.Its preparation process is: at first need polyvinylidene fluoride resin is dissolved in certain solvent, by adding pore-foaming agent, materials such as surfactant prepare perforated membrane.The disadvantage of this film-forming process is to need with a large amount of solvents environment is had certain pollution, and the film of preparation must be kept in the solvent transportation inconvenience.Because film mainly is to utilize the immersion precipitation preparation, the film isotropism of gained does not have orientation, and the mechanical performance of film is relatively poor.For improving the shortcoming of this filming technology, people have attempted other and have prepared the method for Kynoar hollow-fibre membrane, and thermally induced phase separation (TIPS) is wherein topmost a kind of.U.S. Patent No. 5022990 discloses a kind of new method for preparing polyvinylidene fluoride porous film, this method is with polyvinylidene fluoride resin and organic liquid and inorganic granular mixing, then the blend of gained is melt extruded into the film of hollow fiber, tubulose or flat, at last organic liquid and inorganic pellet are extracted.The internal diameter of prepared film is 1.10mm, and wall thickness is 0.45mm, and average pore size is 0.05-5m μ, and fracture strength is 7-20MPa.The shortcoming of the method is to increase to above-mentioned value when above when the film internal diameter, and the resistance to pressure of this film, water flux can reduce, and along with the increase membranous wall attenuation of film internal diameter.A kind ofly not only to have had bigger internal diameter but also had excellent resistance to pressure and a water flux higher in order preparing, and to be suitable for handling the porous polyvinylidene fluoride resin film of the hollow fiber of high viscosity liquid.The preparation Kynoar that Chinese patent No.98807444 and U.S. Patent No. 6299773 disclose a kind of improved TIPS method prepares the technology of hollow-fibre membrane.The method of this technology is: with polyvinylidene fluoride resin and organic liquid and inorganic granular mixing, under 60 ℃ or higher temperature more than the fusing point of described resin,, extrudes the blend heating and melting, and hollow molding, the air cooling is reeled.From the hollow fiber type extrudate, extract organic liquid and inorganic pellet then.Prepared in this way hollow-fibre membrane has tridimensional network, and its internal diameter is 1.5-5mm, and wall thickness is 0.5-2mm, and average pore size is 0.10-0.40 μ m.This film has bigger internal diameter and excellent resistance to pressure and water penetration, is applicable to the filtration of high viscosity liquid.The shortcoming that the TIPS legal system is equipped with the maximum of polyvinylidene fluoride porous film be manufacturing cost than higher, and need extraction.
Kynoar and polypropylene, polyethylene is similar also is a kind of crystalline polymer, has polymorphic structures such as α, β, γ, but is generally obtaining the α spherulitic crystal structure under the processing conditions usually.U.S. Patent No. 3558764 and No.4530809 have reported the method for preparing polypropylene, polyethylene hollow fiber film by melt spinning-cold stretch technology respectively.The principle of its film forming mainly is can form the lamellar structure that hangs down and be arranged in parallel as for fiber axis according to this type of macromolecular material after melt extruding under the stress field.This doughnut with lamellar structure is under extended state, and lamellar structure is understood separated and formed microcellular structure.Whole film-forming process does not need to add any pore-forming auxiliary agent, does not need solvent yet.These two patents of invention mainly are that the hard elastics character of utilizing polypropylene, polythene material to have prepares hollow fiber microporous membrane.Kynoar is a kind of polymer of low-surface-energy, if with the preparation of same technology, easily forms and cortex construction and be difficult to obtain microcellular structure.We obtain lamellar structure by the crystallization control condition, can be by following approach system film: by the control thermograde, the minimizing cortex construction prepares the film with symmetrical holes structure, can be used for aspects such as hyperfiltration; Do not control the attenuate cortex construction, the preparation asymmetric membrane is as gas separation, infiltrating and vaporizing membrane; Destroy cortex construction system film by improving draw ratio.Yet there are no patent report about the film-forming process for preparing the Kynoar hollow-fibre membrane with melt spinning-drawing process at present.
Summary of the invention
The purpose of this invention is to provide a kind of method for preparing the Kynoar hollow-fibre membrane with melt-spun-pulling method.
The step of method is:
1) with melt index is the polyvinylidene fluoride resin of 2-6g/min, heating and melting under 210-240 ℃ of temperature;
2) Kynoar after the fusion is extruded into hollow fiber, by the cooling pipe cooling, the radial symmetry gradient of cooling pipe is less than 20 ℃/cm, and average axial temperature gradient descends less than 30 ℃/m, and the draw ratio that melt extrudes process is more than 1000;
3) hollow fiber Kynoar extrudate is wound into silk, undrawn yarn is 110-140 ℃ of following heat treatment;
4) with the Kynoar hollow fibre filament after the heat treatment, to stretch greater than the 10mm/min rate of extension, the Kynoar hollow fibre filament after the stretching carries out thermal finalization under the tensile stress effect, and setting temperature is 130-150 ℃, shaping time 〉=1 hour.
The present invention directly uses melt spinning-drawing process to prepare the Kynoar hollow-fibre membrane, film-forming process without any need for solvent and additive, filming technology is simple and easy to operate.The characteristics of the Kynoar hollow-fibre membrane that this law is prepared are that tensile break strength is 100-150MPa, are higher than far away with phase inversion and the prepared hollow-fibre membrane of thermally induced phase separation.At 25%-60%, the average pore size of micropore is at 0.01-0.1 μ m with the porosity of the hollow-fibre membrane of melt-spun-pulling method preparation, and air penetrability is 1 * 10
-2-1 * 10
-6Cm
3(STP)/cm
2ScmHg.The internal diameter of this film is 150～400 μ m, and wall thickness is 30～60 μ m.This hollow-fibre membrane is expected to be used for preparing devices such as microfilter, film distillation, membrane extraction, membrane contactor, is used for aspects such as chemical industry, environmental protection, biochemical pharmacy, health care and industry water purified treatment.
Description of drawings
Accompanying drawing is a process chart of the present invention.
The specific embodiment
Process route of the present invention as shown in the figure, adopting pure polyvinylidene fluoride resin is spinning material, does not add any pore-forming auxiliary agent and organic solvent, but directly by melt extruding, hollow molding, technologies such as coiling prepare doughnut.Then by heat treatment, cold stretch, hot-stretch, technologies such as thermal finalization prepare the Kynoar hollow fiber microporous membrane.
Used its melt index of polyvinylidene fluoride resin (MI) of the present invention is per 10 minutes 2-6 grams, and weight average molecular weight range is at 100000-500000.The spinning temperature of spinning head of the present invention satisfy spinnable condition should be low as much as possible, best spinning temperature is between 210-240 ℃.The linear velocity that Kynoar melt extrudes has the size of measurement gear pump and the area of section decision of hollow spinning head, and spinning head adopts the used spinning head type of preparation doughnut usually.In order to make doughnut have certain crystalline orientation degree, should increase draw ratio (ratio of the convoluting speed of doughnut and spinning head extrusion linear speed) as much as possible.In order to reduce the influence that cortex construction forms the doughnut membrane micropore, doughnut needed before entering blowing duct through one section temperature gradient zone by the heating jacket control of different capacity after spinning head is extruded in addition.Enter cooling air channel then, doughnut is fully cooled off, typing fully, hollow fibre filament just is not easy distortion when reeling like this.
The draw ratio of melt-spun process should be preferably in more than 1000 greater than 500 among the present invention, and the cross-sectional area of extruding of spinning head should be greater than 0.1cm
2Entering blowing duct radial symmetry gradient before in the melt spinning process should be less than 20 ℃/cm, and average axial temperature gradient should be less than 30 ℃/m.
The hollow-fibre membrane that the present invention obtains, need heat-treat technology to improve its degree of crystallinity, generally under 110-140 ℃ of condition, heat-treat, heat treatment time 〉=2h, the degree of crystallinity of fiber and elastic recovery rate all are greatly improved after the heat treatment, degree of crystallinity brings up to 60% by 48%, and elastic recovery rate is more than 80%.Stretching need be carried out under certain temperature and rate of extension.Stretch to divide two stages to carry out, at first at room temperature carry out cold drawnly, extensibility is 10-50%, carries out hot-stretch then, and stretch rate is 50-290%.General extensibility is controlled at 100%-300%, and draft temperature is preferably within 100 ℃, and rate of extension is greater than 10mm/min.Heat setting temperature is controlled between 130-150 ℃, shaping time 〉=1h.
The present invention at first makes the abundant fusion of polyvinylidene fluoride resin, extrudes and hollow molding, and reeling after the air cooling of different temperatures gradient zones obtains hollow fibre filament, heat-treats then.Hollow fibre filament after the heat treatment stretches under certain draft temperature and rate of extension and carries out thermal finalization and handle, and can get the Kynoar hollow-fibre membrane at last.
Below in conjunction with hereinafter embodiment the present invention is done more detailed description, but described embodiment is not construed as limiting the invention.Determine performance described herein by following method.
(1) weight average molecular weight (Mw): measure according to the molecular weight of polystyrene by GPC.
GPC instrument: WATERS high performance liquid chromatograph pillar: GMHXL
Solvent: N, N-dimethylacetylamide temperature: 25 ℃
(2) air penetrability J
Instrument: air penetrability instrument
Sample preparation: get 4 of HDPE hollow-fibre membranes, every is about 0.5m, passes support and with epoxy resin its lower end aperture seal is fixed, and makes that the hollow fiber microporous membrane length overall of test is 4 * 20cm, solidifies 12h,
Condition: carrier gas is a nitrogen, room temperature measuring.
V-is for seeing through the volume (cm of nitrogen
3)
P-is nitrogen gas pressure (mmHg)
Internal surface area (the cm of A-hollow-fibre membrane
2), wherein
A＝π·D·h·n(cm
2)??????????????????????????(2)
The h-effective length, D-doughnut internal diameter,
N-tunica fibrosa quantity, t-sees through the time (s)
(3) average pore size
Mainly by air penetrability J and porosity P
rMeasure, can try to achieve the average pore size of micropore by following formula.
Wherein,
R-pore radius (m)
η-through gas viscosity
δ-microporous barrier gets wall thickness m
J-air penetrability (cm
3/ cm
2ScmHg)
P
r-porosity
Porosity is mainly measured according to densimetry, and step is as follows:
Get the nascent doughnut of certain-length, put into the drier constant weight after the drying and record its external diameter, obtain fiber volume, record quality of fiber simultaneously, divided by volume, promptly can obtain the density (ρ of doughnut by quality
0), the density (ρ) of the doughnut after can obtaining stretching with quadrat method can be calculated porosity (P by following formula
r):
Embodiment 1
With Kynoar (Zhejiang Province blue-green environmental protection high-tech Co., Ltd, melt index 3.0g/10min) carries out melt spinning, the melt spinning condition is as follows: the hollow spinning head has the bushing type spinning head of air supply pipe in being, the central gas-supply pipe feeds nitrogen, and pressure is 35 millimeters of water.The spinning temperature of spinning head is 230 ℃.Melt extruding the radial symmetry gradient that thing enters before the blowing duct is 15 ℃/cm, and average axial temperature gradient is 25 ℃/m.The coiling speed of hollow fibre filament is 90m/min, and draw ratio is 1000.With the preparation the doughnut undrawn yarn at 130 ℃ of heat treatment 24h, then directly stretch.Stretching condition is: at first cold drawn about 20% with the rate of extension of 5cm/min under 40 ℃, carry out hot-drawn with same speed then under 90 ℃, stretch rate is 140% altogether.Place 140 ℃ air blast to heat in the drying room then under the fixed length condition, thermal finalization 1h can make the Kynoar hollow fiber microporous membrane.
So the character of the hollow-fibre membrane that obtains is shown in Table 1.
Embodiment 2
With Kynoar (Zhejiang Province blue-green environmental protection high-tech Co., Ltd, melt index 3.0g/10min) carries out melt spinning, the melt spinning condition is as follows: the hollow spinning head has the bushing type spinning head of air supply pipe in being, the central gas-supply pipe feeds nitrogen, and pressure is 30 millimeters of water.The spinning temperature of spinning head is 226 ℃.Melt extruding the radial symmetry gradient that thing enters before the blowing duct is 15 ℃/cm, and average axial temperature gradient is 25 ℃/m.The coiling speed of hollow fibre filament is 130m/min, and draw ratio is 1400.With the preparation the doughnut undrawn yarn at 130 ℃ of heat treatment 24h, then directly stretch.Stretching condition is: at first cold drawn about 30% with the rate of extension of 6cm/min under 40 ℃, carry out hot-drawn with same speed then under 90 ℃, stretch rate is 150% altogether.Place 145 ℃ air blast to heat in the drying room then under the fixed length condition, thermal finalization 1h can make the Kynoar hollow fiber microporous membrane.
So the character of the hollow-fibre membrane that obtains is shown in Table 1.
Embodiment 3
With Kynoar (Zhejiang Province blue-green environmental protection high-tech Co., Ltd, melt index 3.0g/10min) carries out melt spinning, the melt spinning condition is as follows: the hollow spinning head has the bushing type spinning head of air supply pipe in being, the central gas-supply pipe feeds nitrogen, and pressure is 30 millimeters of water.The spinning temperature of spinning head is 220 ℃.Melt extruding the radial symmetry gradient that thing enters before the blowing duct is 15 ℃/cm, and average axial temperature gradient is 25 ℃/m.The coiling speed of hollow fibre filament is 140m/min, and draw ratio is 1500.With the preparation the doughnut undrawn yarn at 130 ℃ of heat treatment 24h, then directly stretch.Stretching condition is: at first cold drawn about 30% with the rate of extension of 10cm/min under 40 ℃, carry out hot-drawn with same speed then under 90 ℃, stretch rate is 170% altogether.Place 145 ℃ air blast to heat in the drying room then under the fixed length condition, thermal finalization 1h can make the Kynoar hollow fiber microporous membrane.
So the character of the hollow-fibre membrane that obtains is shown in Table 1.
Embodiment 4
With Kynoar (Zhejiang Province blue-green environmental protection high-tech Co., Ltd, melt index 2.16g/10min) carries out melt spinning, the melt spinning condition is as follows: the hollow spinning head has the bushing type spinning head of air supply pipe in being, the central gas-supply pipe feeds nitrogen, and pressure is 30 millimeters of water.The spinning temperature of spinning head is 234 ℃.Melt extruding the radial symmetry gradient that thing enters before the blowing duct is 15 ℃/cm, and average axial temperature gradient is 25 ℃/m.The coiling speed of hollow fibre filament is 130m/min, and draw ratio is 1400.With the preparation the doughnut undrawn yarn at 135 ℃ of heat treatment 12h, then directly stretch.Stretching condition is: at first cold drawn about 30% with the rate of extension of 10cm/min under 40 ℃, carry out hot-drawn with same speed then under 90 ℃, stretch rate is 170% altogether.Place 145 ℃ air blast to heat in the drying room then under the fixed length condition, thermal finalization 1h can make the Kynoar hollow fiber microporous membrane.
So the character of the hollow-fibre membrane that obtains is shown in Table 1.
Embodiment 5 (comparative example)
Except the coiling speed of hollow fibre filament is 150m/min, draw ratio is outside 1700, and all the other steps that repeat examples 2 prepare hollow fibre filament.
So the character of the hollow-fibre membrane that obtains is shown in Table 1.
Embodiment 6 (comparative example)
Except the spinning temperature of spinning head at 226 ℃, outside 135 ℃ of heat treatment 24h of the heat treatment temperature of hollow fibre filament, all the other steps that repeat examples 4 prepare hollow fibre filament.
So the character of the hollow-fibre membrane that obtains is shown in Table 1.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment (comparative example) 5 | Embodiment (comparative example) 6 | |
| Internal diameter (μ m) | ????345 | ????330 | ????324 | ????335 | ????324 | ????328 |
| Wall thickness (μ m) | ????54 | ????47 | ????39 | ????44 | ????43 | ????40 |
| Porosity (%) | ????29 | ????39 | ????59 | ????44 | ????43 | ????45 |
| Average pore size (μ m) | ????0.012 | ????0.027 | ????0.057 | ????0.029 | ????0.036 | ????0.044 |
| Air penetrability (the cm of elementary membrane area 3/cm 2·s·cmHg) | ????9.78× ????????10 -5 | ????6.33× ????????10 -4 | ????4.69× ????????10 -3 | ????8.64× ????????10 -4 | ????1.35× ????????10 -3 | ????2.14× ????????10 -3 |
| Fracture strength (MPa) | ????147 | ????140 | ????129 | ????136 | ????119 | ????137 |
Claims (2)
1. one kind prepares the method for Kynoar hollow-fibre membrane with melt-spun-pulling method, it is characterized in that the step of method is:
1) with melt index is the polyvinylidene fluoride resin of 2-6g/min, heating and melting under 210-240 ℃ of temperature;
2) Kynoar after the fusion is extruded into hollow fiber, by the cooling pipe cooling, the radial symmetry gradient of cooling pipe is less than 20 ℃/cm, and average axial temperature gradient descends less than 30 ℃/m, and the draw ratio that melt extrudes process is more than 1000;
3) hollow fiber Kynoar extrudate is wound into silk, undrawn yarn is 110-140 ℃ of following heat treatment;
4) with the Kynoar hollow fibre filament after the heat treatment, to stretch greater than the 10mm/min rate of extension, the Kynoar hollow fibre filament after the stretching carries out thermal finalization under the tensile stress effect, and setting temperature is 130-150 ℃, shaping time 〉=1 hour.
2. a kind of method for preparing the Kynoar hollow-fibre membrane with melt-spun-pulling method according to claim 1, it is characterized in that, the drawing process of said hollow fibre filament is: at first at cold drawn 10%-50% below 40 ℃, then at 50-100 ℃ of following hot-drawn 50%-290%.
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|---|---|---|---|
| CN 200410067007 CN1281301C (en) | 2004-09-30 | 2004-09-30 | Method for preparing for polyvinylidene fluoride hollow fiber microporous film by melt spinning-pull stretching method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410067007 CN1281301C (en) | 2004-09-30 | 2004-09-30 | Method for preparing for polyvinylidene fluoride hollow fiber microporous film by melt spinning-pull stretching method |
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| Publication Number | Publication Date |
|---|---|
| CN1621139A true CN1621139A (en) | 2005-06-01 |
| CN1281301C CN1281301C (en) | 2006-10-25 |
Family
ID=34764980
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|---|---|---|---|
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2004
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