CN1621138A - Method for preparing polyvinylidene fluoride hollow fiber microporous film by microscopic phase separating method - Google Patents
Method for preparing polyvinylidene fluoride hollow fiber microporous film by microscopic phase separating method Download PDFInfo
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- CN1621138A CN1621138A CN 200410067002 CN200410067002A CN1621138A CN 1621138 A CN1621138 A CN 1621138A CN 200410067002 CN200410067002 CN 200410067002 CN 200410067002 A CN200410067002 A CN 200410067002A CN 1621138 A CN1621138 A CN 1621138A
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- kynoar
- hollow fiber
- phase separating
- polyvinylidene fluoride
- microporous membrane
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- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 12
- 239000012510 hollow fiber Substances 0.000 title claims description 28
- 239000000835 fiber Substances 0.000 claims abstract description 37
- 238000002844 melting Methods 0.000 claims abstract description 3
- 230000008018 melting Effects 0.000 claims abstract description 3
- 239000012982 microporous membrane Substances 0.000 claims description 21
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 11
- 239000008188 pellet Substances 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 10
- 230000003179 granulation Effects 0.000 claims description 10
- 238000007493 shaping process Methods 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 4
- 229920006217 cellulose acetate butyrate Polymers 0.000 claims description 4
- 239000005543 nano-size silicon particle Substances 0.000 claims description 4
- 238000007664 blowing Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 230000004927 fusion Effects 0.000 claims description 3
- 239000011368 organic material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 claims description 2
- 239000004354 Hydroxyethyl cellulose Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920006184 cellulose methylcellulose Polymers 0.000 claims description 2
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 1
- 150000004706 metal oxides Chemical class 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 claims 1
- 229920006304 triacetate fiber Polymers 0.000 claims 1
- 238000009987 spinning Methods 0.000 abstract description 46
- 239000000203 mixture Substances 0.000 abstract description 12
- 239000011148 porous material Substances 0.000 abstract description 9
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- 239000012528 membrane Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 235000012489 doughnuts Nutrition 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 13
- 238000005516 engineering process Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000002145 thermally induced phase separation Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001891 gel spinning Methods 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
- 230000035515 penetration Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Landscapes
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The present invention is micro phase separating process of preparing hollow microporous polyvinylidene fluoride fiber film. The present invention features that some hydrophilic matter with relatively high surface energy and polyvinylidene fluoride are molten and mixed, and the mixture is prepared into the hollow microporous polyvinylidene fluoride fiber film through melting spinning and stretching. The hollow microporous polyvinylidene fluoride fiber film features the improved hydrophobic property, contact angle lowering by over 20 deg, tensile break strength of 100-150 MPa, elongation at breaking of 150-400 %, porosity of 30-70 %, average pore size of 0.01-0.2 micron, air penetrability of 0.0001-0.1 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 fiber microporous membrane with microscopic phase separating 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.
The Kynoar hollow fiber microporous membrane mainly prepares by the solution phase inversion the earliest.In Chinese patent Nos.95117497 and 98103153, describe in detail with wet method and dry-wet spinning technology and prepare the Kynoar hollow fiber microporous membrane.The disadvantage of this filming technology 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.After this people attempt other filming technology, and wherein thermally induced phase separation is first-selected film-forming method.U.S. Patent No. 5022990 discloses a kind of new method of utilizing thermally induced phase separation to prepare 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.For problem Chinese patent No.98807444 and the U.S. Patent No. 6299773 of improving this filming technology existence discloses a kind of improved technology for preparing Kynoar doughnut perforated membrane with thermally induced phase separation.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.This film has bigger internal diameter and excellent resistance to pressure and water penetration, is applicable to the filtration of high viscosity liquid.
The method of utilizing the micron-scale phase separation behavior to prepare microporous barrier is not seen patent report.The pore forming process of this method is, at first a kind of hydrophilic organic or inorganic substances and fluoropolymer resin carried out melt blending, and granulation, prepares hollow fibre filament by melt-spinning technology then.When hollow fibre filament was stretched, the two-phase interface of polymer and blend material was easy to generate the slit, can form the micropore of many perforation tube walls, prepares hollow fiber microporous membrane with this.The Kynoar hollow fiber microporous membrane of preparation with the microporous barrier of melt spinning-stretching technique preparation, all wants excellent at aspects such as pore size and hydrophilies than only in this way.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing microscopic phase separating method to prepare the Kynoar hollow fiber microporous membrane.
The step of method is:
1) with melt index be the polyvinylidene fluoride resin of 2-6g/min and hydrophilic organic material or inorganic pellet at 200-230 ℃ of following melt blending, and granulation, heating and melting under 210-240 ℃ of temperature then;
2) Kynoar after the fusion is extruded into hollow fiber, needed the heat-preservation cylinder through 20-50 centimetre before entering blowing duct, enter the cooling air channel cooling then, 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.
Advantage of the present invention is:
Micron-scale phase separation behavior according to two-phase interface obtains microcellular structure.The expense of additive is little, and raw material is easy to get.Preparation process is without any need for solvent, and filming technology is simple and easy to operate.The tensile break strength of gained hollow-fibre membrane of the present invention is 100-150MPa, and elongation at break is 150-400%.The porosity of film is 30%-70%, and average pore size is at 0.01-0.2 μ m, and air penetrability is 1 * 10
-4～1 * 10
-1Cm
3/ cm
2ScmHg.The internal diameter of this film is 150～400 μ m, and wall thickness is 30～60 μ m.
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 Figure 1.Concrete step is that the blend pellet of hydroaropic substance and Kynoar is added in the spinning-drawing machine, through melt extruding, and hollow molding, technologies such as coiling prepare doughnut.By heat treatment, stretch then, 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 2-6g/10min, weight average molecular weight (M
w) about 100000 to 500000.The used hydroaropic substance of the present invention mainly is cellulose acetate butyrate, CMC, hydroxyethylcellulose, cellulose diacetate, Triafol T, polyethylene glycol and some inorganic nanometer oxides, comprises nano silicon, titanium dioxide and nanometer α-alchlor.The spinning temperature of spinning head is more than the Kynoar melt temperature among the present invention, but in order to satisfy spinnable condition, spinning temperature should be low as much as possible, and 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.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 the 20-50 millimeter of water.In addition, in order to reduce the influence that cortex construction forms the doughnut micropore, doughnut is after spinning head is extruded, before entering blowing duct, need heat-preservation cylinder through 20-50 centimetre, enter cooling air channel then, doughnut is fully cooled off, and typing fully is not easy distortion like this when the coiling doughnut.
The hydroaropic substance that adds in the Kynoar is except the cortex construction that changes doughnut, meeting and the behavior of Kynoar generation micron-scale phase separation in drawing process, help the formation of micropore on the hollow fiber walls, but also help improving the hydrophily of film, contact angle descends 〉=20 °.The adding of this material needs certain ratio, and weight percentage can not be greater than 1%.This be because when its content above 1% the time, the spinning phenomenon that breaks end easily.When its addition very little the time, the effect that generates micropore is not again fine.Thereby the addition of control hydroaropic substance is important to the generation of micropore.
The draw ratio of the draw ratio spinning process of the spinning of spinning process of the present invention is greater than 500, is preferably in more than 1000, and the cross-sectional area of extruding of spinning head should be greater than 0.1 centimetre
2The hollow-fibre membrane that the present invention obtains need be heat-treated under 110-140 ℃ of condition, to improve the degree of orientation and the degree of crystallinity of doughnut.Stretching need be carried out under certain temperature and rate of extension, and general extensibility is controlled at 100-300%, and draft temperature is between 20-100 ℃, and rate of extension is greater than 10mm/min, and heat setting temperature is controlled between 130-150 ℃, and shaping time is not less than 1h.
Used polyvinylidene fluoride resin among the present invention comprises the homopolymers and the copolymer of Kynoar, the homopolymers of first-selected Kynoar.Its copolymer mainly contains poly-(biasfluoroethylene-hexafluoropropylene), poly-(vinylidene-CTFE), poly-(vinylidene-ethene), poly-(vinylidene-propylene), poly-(biasfluoroethylene-hexafluoropropylene-tetrafluoroethene) etc.
The present invention at first makes the Kynoar and the hydroaropic substance of certain percentage composition carry out melt blending, and granulation.Blend with both adds in the melt spinning machine then, after abundant fusion, it is extruded and hollow molding, reels after the air cooling, and the hollow fibre filament that obtains is heat-treated.Then the hollow fibre filament after the heat treatment is stretched under uniform temperature and rate of extension and carry out thermal finalization and handle.Can obtain the hollow fiber microporous membrane that we need 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 blending with cellulose diacetate (Wuxi Chemical Research and Design Inst.) at 200 ℃, the weight percentage of cellulose diacetate is 0.03%, and granulation.Then the blend pellet is added in the spinning-drawing machine, prepare hollow-fibre membrane through melt spinning-drawing process.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 215 ℃.The coiling speed of hollow fibre filament is 100m/min, and draw ratio is 1100.The doughnut undrawn yarn of preparation is heat-treated 24h at 125 ℃, then directly stretch.Stretching condition is: the rate of extension with 3cm/min under 90 ℃ stretches, and extensibility is 140%.Place under the fixed length condition then in 140 ℃ the air blast heating drying room and carry out thermal finalization, shaping time 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 blending with cellulose acetate butyrate (Wuxi Chemical Research and Design Inst.) at 210 ℃, the weight percentage of cellulose acetate butyrate is 0.03%, and granulation.Then the blend pellet is added in the spinning-drawing machine, prepare hollow-fibre membrane through melt spinning-drawing process.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 33 millimeters of water.The spinning temperature of spinning head is 216 ℃.The coiling speed of hollow fibre filament is 140m/min, and draw ratio is 1500.The doughnut undrawn yarn of preparation is heat-treated 12h at 135 ℃, then directly stretch.Stretching condition is: the rate of extension with 4cm/min under 90 ℃ stretches, and extensibility is 160%.Place under the fixed length condition then in 140 ℃ the air blast heating drying room and carry out thermal finalization, shaping time 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 blending with CMC (Wuxi Chemical Research and Design Inst.) at 215 ℃, the weight percentage of CMC is 0.04%, and granulation.Then the blend pellet is added in the spinning-drawing machine, prepare hollow-fibre membrane through melt spinning-drawing process.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 224 ℃.The coiling speed of hollow fibre filament is 140m/min, and draw ratio is 1500.The doughnut undrawn yarn of preparation is heat-treated 12h at 140 ℃, then directly stretch.Stretching condition is: the rate of extension with 3cm/min under 90 ℃ stretches, and extensibility is 150%.Place under the fixed length condition then in 140 ℃ the air blast heating drying room and carry out thermal finalization, shaping time 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 2.6g/10min) carries out melt blending with nano silicon (Zhoushan Tomorrow Nanomaterials Co., Ltd) at 220 ℃, the weight percentage of nano silicon is 0.03%, and granulation.Then the blend pellet is added in the spinning-drawing machine, prepare hollow-fibre membrane through melt spinning-drawing process.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 33 millimeters of water.The spinning temperature of spinning head is about 236 ℃.The coiling speed of hollow fibre filament is 130m/min, and draw ratio is 1400.The doughnut undrawn yarn of preparation is heat-treated 12h at 130 ℃, then directly stretch.Stretching condition is: the rate of extension with 4cm/min under 90 ℃ stretches, and extensibility is 140%.Place under the fixed length condition then in 135 ℃ the air blast heating drying room and carry out thermal finalization, time typing 〉=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
With Kynoar (Zhejiang Province blue-green environmental protection high-tech Co., Ltd, melt index 2.6g/10min) carries out melt blending with nanometer α-alchlor (Zhoushan Tomorrow Nanomaterials Co., Ltd) at 225 ℃, the weight percentage of nanometer α-alchlor is 0.04%, and granulation.Then the blend pellet is added in the spinning-drawing machine, prepare hollow-fibre membrane through melt spinning-drawing process.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 33 millimeters of water.The spinning temperature of spinning head is 233 ℃.The coiling speed of hollow fibre filament is 130m/min, and draw ratio is 1400.The doughnut undrawn yarn of preparation is heat-treated 12h at 140 ℃, then directly stretch.Stretching condition is: the rate of extension with 4cm/min under 90 ℃ stretches, and extensibility is 150%.Place under the fixed length condition then in 145 ℃ the air blast heating drying room and carry out thermal finalization, shaping time 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 6
With Kynoar (Zhejiang Province blue-green environmental protection high-tech Co., Ltd, melt index 2.6g/10min) carries out melt blending with nano titanium oxide (Zhoushan Tomorrow Nanomaterials Co., Ltd) at 223 ℃, the weight percentage of nano titanium oxide is 0.04%, and granulation.Then the blend pellet is added in the spinning-drawing machine, prepare hollow-fibre membrane through melt spinning-drawing process.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 ℃.The coiling speed of hollow fibre filament is 130m/min, and draw ratio is 1400.The doughnut undrawn yarn of preparation is heat-treated 12h at 135 ℃, then directly stretch.Stretching condition is: the rate of extension with 4cm/min under 90 ℃ stretches, and extensibility is 160%.Place under the fixed length condition then in 150 ℃ the air blast heating drying room and carry out thermal finalization, shaping time 1h can make the Kynoar hollow fiber microporous membrane.
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 5 | Embodiment 6 | |
| Internal diameter (μ m) | ????352 | ????325 | ????310 | ????350 | ????347 | ????343 |
| Wall thickness (μ m) | ????53 | ????42 | ????39 | ????48 | ????47 | ????45 |
| Porosity (%) | ????33 | ????61 | ????51 | ????39 | ????41 | ????42 |
| Average pore size (μ m) | ????0.050 | ????0.17 | ????0.15 | ????0.060 | ????0.078 | ????0.084 |
| Air penetrability (the cm of elementary membrane area 3/cm 2·s·cmHg) | ????1.58× ????????10 -3 | ????4.33× ????????10 -2 | ????3.17× ????????10 -2 | ????3.25× ????????10 -3 | ????5.35× ????????10 -3 | ????6.87× ????????10 -3 |
| Fracture strength (MPa) | ????141 | ????124 | ????117 | ????135 | ????132 | ????128 |
Claims (5)
1. one kind prepares the method for Kynoar hollow fiber microporous membrane with microscopic phase separating method, it is characterized in that the step of method is:
1) with melt index be the polyvinylidene fluoride resin of 2-6g/min and hydrophilic organic material or inorganic pellet at 200-230 ℃ of following melt blending, and granulation, heating and melting under 210-240 ℃ of temperature then;
2) Kynoar after the fusion is extruded into hollow fiber, before entering blowing duct, needs heat-preservation cylinder, enter the cooling air channel cooling then through 20-50 centimetre; 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 fiber microporous membrane with microscopic phase separating method according to claim 1, it is characterized in that said hydrophilic organic material is: cellulose acetate butyrate, CMC, hydroxyethylcellulose, cellulose diacetate, triacetate fiber or polyethylene glycol.
3. a kind of method for preparing the Kynoar hollow fiber microporous membrane with microscopic phase separating method according to claim 1, it is characterized in that said hydrophilic inorganic pellet mainly comprises: nano silicon, titanium dioxide or α-alchlor metal oxide nano-material.
4. according to claim 1ly a kind ofly prepare the method for Kynoar hollow fiber microporous membrane, it is characterized in that the weight percentage of said hydroaropic substance should be less than 1% with microscopic phase separating method.
5. according to claim 1ly a kind ofly prepare the method for Kynoar hollow fiber microporous membrane, it is characterized in that total extensibility of said Kynoar hollow fibre filament is 100%-300% with microscopic phase separating method.
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|---|---|---|---|
| CN 200410067002 CN1270814C (en) | 2004-09-30 | 2004-09-30 | Method for preparing polyvinylidene fluoride hollow fiber microporous film by microscopic phase separating method |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100384521C (en) * | 2005-09-13 | 2008-04-30 | 浙江大学 | Method for improving hydrophilicity of polymer porous membrane by dentritic branching molecule |
| CN101590374B (en) * | 2008-05-27 | 2012-09-19 | 广州美能材料科技有限公司 | Polyvinylidene fluoride hollow fiber film and preparation method thereof |
| CN102851763A (en) * | 2012-08-09 | 2013-01-02 | 广州中国科学院先进技术研究所 | Integrated hollow fiber membrane spinning machine |
| CN104667764A (en) * | 2015-01-30 | 2015-06-03 | 华南理工大学 | Polyvinylidene fluoride film enhanced by nano microcrystalline cellulose as well as preparation method and application of polyvinylidene fluoride film enhanced by nano microcrystalline cellulose |
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2004
- 2004-09-30 CN CN 200410067002 patent/CN1270814C/en not_active Expired - Fee Related
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| CN100384521C (en) * | 2005-09-13 | 2008-04-30 | 浙江大学 | Method for improving hydrophilicity of polymer porous membrane by dentritic branching molecule |
| CN101590374B (en) * | 2008-05-27 | 2012-09-19 | 广州美能材料科技有限公司 | Polyvinylidene fluoride hollow fiber film and preparation method thereof |
| CN102851763A (en) * | 2012-08-09 | 2013-01-02 | 广州中国科学院先进技术研究所 | Integrated hollow fiber membrane spinning machine |
| CN104667764A (en) * | 2015-01-30 | 2015-06-03 | 华南理工大学 | Polyvinylidene fluoride film enhanced by nano microcrystalline cellulose as well as preparation method and application of polyvinylidene fluoride film enhanced by nano microcrystalline cellulose |
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| EP3466527B1 (en) * | 2016-05-31 | 2024-04-03 | Toray Industries, Inc. | Porous hollow-fiber membrane and production process therefor |
| CN106268353A (en) * | 2016-09-23 | 2017-01-04 | 广州仕瀚环保科技有限公司 | Bacteriostatic activated carbon film silk |
| CN106310969A (en) * | 2016-09-23 | 2017-01-11 | 广州仕瀚环保科技有限公司 | Activated-carbon membrane filament |
| CN107661699A (en) * | 2017-09-30 | 2018-02-06 | 合肥凯华环保科技有限公司 | A kind of preparation technology of waste water deaminizing processing hydrophobic membrane |
| CN109078502A (en) * | 2018-08-15 | 2018-12-25 | 新疆水处理工程技术研究中心有限公司 | A kind of production method of casting solution, casting film liquor manufacture method and tubular membrane |
| CN110180401A (en) * | 2019-06-28 | 2019-08-30 | 天津工业大学 | A kind of preparation method of (per) fluoropolymer hollow-fibre membrane |
| CN110180401B (en) * | 2019-06-28 | 2021-09-17 | 天津工业大学 | Preparation method of perfluoropolymer hollow fiber membrane |
| CN112853626A (en) * | 2019-11-26 | 2021-05-28 | 浙江省化工研究院有限公司 | ECTFE melt-blown film and preparation method thereof |
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