CN105478021A - Preparation technology of PVDF (polyvinylidene fluoride) microporous membrane - Google Patents
Preparation technology of PVDF (polyvinylidene fluoride) microporous membrane Download PDFInfo
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- CN105478021A CN105478021A CN201610019777.1A CN201610019777A CN105478021A CN 105478021 A CN105478021 A CN 105478021A CN 201610019777 A CN201610019777 A CN 201610019777A CN 105478021 A CN105478021 A CN 105478021A
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- polyvinylidene fluoride
- microporous film
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Abstract
The invention relates to the field of microporous membrane preparation, in particular to a preparation technology of a PVDF (polyvinylidene fluoride) microporous membrane. The preparation technology comprises steps as follows: 1) 25-45 parts of PVDF resin are dissolved in 23-68 parts of a dimethylacetamide, dimethylformamide solvent or N-methyl-2-pyrrolidone by weight, stirring is performed at the temperature of 40-72 DEG C for 3-5 h, and an initial solution is obtained; 2) 2-5 parts of polyvinylpyrrolidone and 5-25 parts of polyethylene glycol are added to the initial solution by weight, stirring is performed at the temperature of 50-60 DEG C for 5-7 h, and a first-stage membrane casting solution is obtained; 3) 0.5-1.5 parts of deionized water are added to the first-stage membrane casting solution by weight, stirring is performed at the temperature of 40-60 DEG C for 5-7 h, standing for foam removal is performed for 10-14 h, and a second-stage membrane casting solution is obtained.
Description
Technical field
The present invention relates to microporous barrier and manufacture field, be specifically related to a kind of technology of preparing of polyvinylidene fluoride microporous film.
Background technology
Kynoar (PVDF) is a kind of fluoropolymer of function admirable, vitrification point-39 DEG C, brittle temperature less than-62 DEG C, crystalline melt point about 170 DEG C, and thermal decomposition degree is greater than 310 DEG C; Its mechanical strength is high, has the performances such as self-extinguishment, excellent rigidity, hardness, creep resistant, abrasion performance and cut resistant; Chemical stability is good, can antioxidant, acid, alkali, salt, halogen, aromatic hydrocarbons, the corrosion of fat and chlorinated solvent and swelling, have the uvioresistant of excellence concurrently, gamma-rays and ageing-resistant performance, be thus regarded as the ideal material preparing various diffusion barrier.
At present, the preparation of polyvinylidene fluoride film is mainly prepared by phase separation method (NIPS) and these two kinds of modes of thermally induced phase separation (TIPS).NIPS film-forming method, also known as wet method, its technological process is dissolved in solvent by polymer, form homogeneous phase solution, at this moment the reagent stronger with solvent intersolubility is slowly added again solvent extraction out, the two phase structure that formation is continuous phase with polymer, solvent is decentralized photo, then except desolventizing, obtain the polymer with certain pore structure.NIPS film-forming method complex process, macroporous structure, film mechanical performance and chemical-resistance poor.The technical process of TIPS film-forming method and principle are more than the fusing point of polymer, and polymer is dissolved in higher boiling, and in the solvent of low volatility, form homogeneous phase solution, then cooling down, in cooling procedure, system can be separated.This process divides two classes, and a class is that solid-liquid phase is separated (being called for short S-L to be separated), and a class is liquid-liquid phase separation (L-L is separated).Control suitable process conditions, after phase-splitting, System forming take polymer as continuous phase, and solvent is the two phase structure of decentralized photo.At this moment select suitable volatile reagent again solvent extraction out, thus obtain the polymer microporous film of certain planform, usual TIPS casting film system all belongs to this situation.
In the earlier patents AU653528 of TIPS method describes, by polyvinylidene fluoride resin and mixture organic diluent, the antioxidant of trace forms fused materials under 220 DEG C of high temperature and partial vacuum, then at 215 DEG C, doughnut is extruded, the hollow-fibre membrane of such formation, porosity is low, and water flux is little.Chinese patent CN1792420A, CN101362057A adopt benzophenone and diphenyl carbonate to be diluent respectively, during Kynoar/diluent system cooling, liquid-liquid phase separation occurs, obtained have high strength, high porosity, high-throughout homogeneous spongelike structure polyvinylidene fluoride film.Adopt the diluent listed by above method or composite thinning agent, homogeneous spongelike structure polyvinylidene fluoride film can be prepared, but obtained film is polyvinylidene fluoride microporous filtering film, cannot obtain the milipore filter that separation accuracy is higher.No. 3-215535, Unexamined Patent discloses a kind of PVDF perforated membrane with larger mechanical strength.In polyvinylidene fluoride resin, mix adjacent benzene class diluent and dewatering nano silicon dioxide granule, extract organic diluent and nano silicon after melt molding at up to 250 DEG C of temperature.Owing to extracting the base extraction of nano silicon process need high concentration, this can reduce elongation at break and the service life of hollow-fibre membrane greatly.
Kynoar as polar polymer when it is dissolved in the mixed solvent be made up of polar solvent and non-solvent, produce strongly interact owing to forming hydrogen bond between the large molecule of PVDF and solvent molecule, heat release during dissolving, dissolution enthalpy Δ H < 0, system free energy reduces (Δ G < 0), and course of dissolution is spontaneous to carry out.Raise with temperature, molecular thermalmotion aggravates, and the warm-up movement ability increase of small molecule solvent and non-solvent is larger, therefore solvent weakens more with the intermolecular Hydrogen bonding forces of non-solvent relative to the Hydrogen bonding forces between PVDF and solvent, be equivalent to the non-solvent amount be concentrated in polymer reduce, non-solvent molecule apparent concentration increases, and then polymer solubility reduces, homogeneous phase casting solution be separated polymer separate out film forming, this is contrary with traditional TIPS legal system film principle, namely when temperature is elevated to a certain critical-temperature, casting solution is separated, namely the decline of temperature rising polymer solubility is separated, such casting solution system is called low critical consolute temperature (LCST) system, phase disengagement method can be described as reverse thermally induced phase separation.
Summary of the invention
Object of the present invention, to solve NIPS film-forming method complex process in background technology, macroporous structure, film mechanical performance and chemical-resistance is poor and traditional TIPS film-forming method energy consumption is large, the problems such as masking cost high and film product filtering accuracy difference, provide a kind of technology of preparing of polyvinylidene fluoride microporous film.
Main points of the present invention are the mixed solution configuring a kind of Kynoar, water-soluble diluent and water-soluble additives, and under lower temperature conditions, solution is stable transparent.After this solution is heated to certain temperature, the instability that solution becomes, can become muddy, generation is separated.By extrusion molding under lower temperature conditions, then enter high temperature gel bath, nascent state film can exchange because of non-solvent and temperature raises and produces phase-splitting, forms microporous barrier.For hymeniderm layer, owing to adopting traditional NIPS solvent, cortex generation phase separation process polymer concentration, higher than usual NIPS process, so cortex is finer and close, has excellent filtering accuracy and mechanical performance.For Asia/supporting layer, because subgrade reverse Thermal inactive process polymer concentration occurs lower than usual TIPS process, so subgrade is more loose and hole connectedness is good, reduce the circulating resistance of subgrade.Therefore relative to NIPS method, prepared PVDF perforated membrane has more excellent mechanical strength and chemical-resistance, relative to TIPS method, has lower energy consumption, lower polymer concentration (cost) and better pore size filter, perforated membrane excellent combination property.
Above-mentioned technical purpose of the present invention is achieved by the following technical programs:
A technology of preparing for polyvinylidene fluoride microporous film, comprises the following steps:
1) be dissolved in 23 ~ 68 parts of dimethylacetylamides, solvent dimethylformamide or 1-METHYLPYRROLIDONEs by 25 ~ 45 parts of polyvinylidene fluoride resins by weight, control temperature, at 40 ~ 72 DEG C, stirs 3 ~ 5 hours, obtains initial soln;
2) in initial soln, add 2 ~ 5 parts of polyvinylpyrrolidones and 5 ~ 25 parts of polyethylene glycol by weight, control temperature, at 50 ~ 60 DEG C, stirs 5 ~ 7 hours, obtains one-level casting solution;
3) in described one-level casting solution, add 0.5 ~ 1.5 part of deionized water by weight, control temperature is at 40 ~ 60 DEG C, and stir 5 ~ 7 hours, standing and defoaming 10 ~ 14 hours, obtains secondary casting solution;
4) extrude from spinning nozzle together with secondary casting solution using dimethylacetamide amine aqueous solution as core liquid, after volatilizing in atmosphere 0.1 ~ 2 second, enter in the gel water-bath of more than 75 DEG C and exchange with non-solvent, swap time is 10 seconds to 20 seconds, obtains primary filament film;
5) after primary filament film is immersed in the water carries out rinsing desolventizing, in feeder, collect and obtain polyvinylidene fluoride microporous film.
As preferably, described step 2) in molecular weight polyethylene glycol be 20000 ~ 50000.
As preferably, described step 2) in polyvinylpyrrolidone be PVP-K17.
As preferably, in dimethylacetamide amine aqueous solution described in described step 4), the mass fraction of dimethylacetylamide is 20 ~ 38wt%.
As preferably, spinning nozzle described in described step 4) is double-deck spinning nozzle, and its internal-and external diameter is 0.7-0.9/1.3-1.5mm.
As preferably, in described step 4), non-solvent is reverse osmosis water (RO water).
As preferably, in described step 5), rinse temperature is 60 DEG C, and collecting temperature is 50 DEG C.
The polyvinylidene fluoride microporous film that the technology of preparing of the polyvinylidene fluoride microporous film according to said method prepares: film-strength 6-8MPa; Membrane aperture 20-80nm; Membrane flux >=500LMH.
In sum, beneficial effect of the present invention:
1. the technology of preparing of a kind of polyvinylidene fluoride microporous film of the present invention, film-forming method energy consumption is little, and masking cost is lower and film product filtering accuracy is strong.
2. the technology of preparing of a kind of polyvinylidene fluoride microporous film of the present invention, technique is simple, and film-strength, flux are high, film mechanical performance and chemical-resistance better.
3. the polyvinylidene fluoride microporous film prepared of the technology of preparing of a kind of polyvinylidene fluoride microporous film of the present invention, cortex is finer and close, there is excellent filtering accuracy and mechanical performance, in subgrade phase separation, polymer concentration is lower, make subgrade more loose and hole connectedness is good, have lower circulating resistance.
Accompanying drawing explanation
Fig. 1 is the sectional drawing of polyvinylidene fluoride microporous film prepared by the embodiment of the present invention 1;
Fig. 2 is the interior cross-sectional side view of polyvinylidene fluoride microporous film prepared by the embodiment of the present invention 1;
Fig. 3 is the outer cross-sectional side view of polyvinylidene fluoride microporous film prepared by the embodiment of the present invention 1;
Fig. 4 is the section amplification figure of polyvinylidene fluoride microporous film prepared by the embodiment of the present invention 1.
Detailed description of the invention
Following specific embodiment is only explanation of the invention; it is not limitation of the present invention; those skilled in the art can make to the present embodiment the amendment not having creative contribution as required after reading this description, as long as but be all subject to the protection of Patent Law in right of the present invention.
Invention is described in detail with embodiment below in conjunction with accompanying drawing.
Embodiment 1:
A technology of preparing for polyvinylidene fluoride microporous film, comprises the following steps:
1) be dissolved in 56.5 parts of dimethylacetamide solvents by 27 parts of polyvinylidene fluoride resins by weight, control temperature, at 70 DEG C, stirs 4 hours, obtains initial soln;
2) in initial soln, add 4.5 parts of PVP-K17 and 13 part PEG35000 by weight, control temperature, at 60 DEG C, stirs 6 hours, obtains one-level casting solution;
3) in described one-level casting solution, add 1 part of deionized water by weight, control temperature is at 55 DEG C, and stir 6 hours, standing and defoaming 12 hours, obtains secondary casting solution;
4) be that the dimethylacetamide amine aqueous solution of 38wt% is extruded together with secondary casting solution as core liquid from double-deck spinning nozzle with mass fraction, the internal-and external diameter of double-deck spinning nozzle is 0.7/1.3mm, volatilize 0.6 second in the air section of 150mm subsequently, enter in the gel water-bath of more than 76 DEG C and non-solvent and exchange heat occur, cause being separated, swap time is 10 seconds, obtains primary filament film;
5) primary filament film is immersed after carrying out rinsing desolventizing in the water of 60 DEG C, in the feeder of 50 DEG C, collect and obtain polyvinylidene fluoride microporous film.
Shown in composition graphs 1 ~ Fig. 4, the polyvinylidene fluoride microporous film that the technology of preparing of the polyvinylidene fluoride microporous film according to said method prepares: film-strength: 5.6MPa, membrane aperture: 48nm, pure water membrane flux: 680Lm
-2h
-1, chemical-resistance: 5000ppm clorox+2wt% NaOH 15 days after-drawing intensity keeps 86%.
Embodiment 2:
A technology of preparing for polyvinylidene fluoride microporous film, comprises the following steps:
1) be dissolved in 46.5 parts of 1-METHYLPYRROLIDONE Solvents Solvent by 42 parts of polyvinylidene fluoride resins by weight, control temperature, at 72 DEG C, stirs 5 hours, obtains initial soln;
2) in initial soln, add 2 parts of PVP-K17 and 8 part PEG20000 by weight, control temperature, at 60 DEG C, stirs 7 hours, obtains one-level casting solution;
3) in described one-level casting solution, add 1.5 parts of deionized waters by weight, control temperature is at 55 DEG C, and stir 7 hours, standing and defoaming 12 hours, obtains secondary casting solution;
4) be that the dimethylacetamide amine aqueous solution of 25wt% is extruded together with secondary casting solution as core liquid from double-deck spinning nozzle with mass fraction, the internal-and external diameter of double-deck spinning nozzle is 0.9/1.5mm, volatilize 0.2 second in the air section of 50mm subsequently, enter in the gel water-bath of more than 78 DEG C, there is non-solvent and exchange heat, cause being separated, swap time is 10 seconds, obtains primary filament film;
5) primary filament film is immersed after carrying out rinsing desolventizing in the water of 60 DEG C, in the feeder of 50 DEG C, collect and obtain polyvinylidene fluoride microporous film.(data need change, to obtain multiple embodiment)
The polyvinylidene fluoride microporous film that the technology of preparing of the polyvinylidene fluoride microporous film according to said method prepares: film-strength: 7.4MPa, membrane aperture: 22nm, pure water membrane flux: 510Lm
-2h
-1, chemical-resistance: 5000ppm clorox+2wt% NaOH 15 days after-drawing intensity keeps 92%.
Embodiment 3:
A technology of preparing for polyvinylidene fluoride microporous film, comprises the following steps:
1) be dissolved in 45 parts of dimethylacetamide solvents by 28 parts of polyvinylidene fluoride resins by weight, control temperature, at 45 DEG C, stirs 5 hours, obtains initial soln;
2) in initial soln, add 3.5 parts of PVP-K17 and 23 part PEG25000 by weight, control temperature, at 50 DEG C, stirs 5 hours, obtains one-level casting solution;
3) in described one-level casting solution, add 0.5 part of deionized water by weight, control temperature is at 45 DEG C, and stir 6 hours, standing and defoaming 14 hours, obtains secondary casting solution;
4) be that the dimethylacetamide amine aqueous solution of 32wt% is extruded together with secondary casting solution as core liquid from double-deck spinning nozzle with mass fraction, the internal-and external diameter of double-deck spinning nozzle is 0.8/1.4mm, volatilize 1.8 seconds in the air section of 300mm subsequently, enter in the gel water-bath of 80 DEG C, there is non-solvent and exchange heat, cause being separated.Swap time is 20 seconds, obtains primary filament film;
5) primary filament film is immersed after carrying out rinsing desolventizing in the water of 60 DEG C, in the feeder of 50 DEG C, collect and obtain polyvinylidene fluoride microporous film.
The polyvinylidene fluoride microporous film that the technology of preparing of the polyvinylidene fluoride microporous film according to said method prepares: film-strength: 6.1MPa, membrane aperture: 42nm, pure water membrane flux: 710Lm
-2h
-1, chemical-resistance: 5000ppm clorox+2wt% NaOH 15 days after-drawing intensity keeps 84%.
Embodiment 4:
A technology of preparing for polyvinylidene fluoride microporous film, comprises the following steps:
1) be dissolved in 54 parts of solvent dimethylformamides by 30 parts of polyvinylidene fluoride resins by weight, control temperature, at 65 DEG C, stirs 3 hours, obtains initial soln;
2) in initial soln, add 2.5 parts of PVP-K17 and 12 part PEG50000 by weight, control temperature, at 60 DEG C, stirs 7 hours, obtains one-level casting solution;
3) in described one-level casting solution, add 1.5 parts of deionized waters by weight, control temperature is at 55 DEG C, and stir 7 hours, standing and defoaming 10 hours, obtains secondary casting solution;
4) be that the dimethylacetamide amine aqueous solution of 25wt% is extruded together with secondary casting solution as core liquid from double-deck spinning nozzle with mass fraction, the internal-and external diameter of double-deck spinning nozzle is 0.7/1.3mm, volatilize 1.2 seconds in the air section of 200mm subsequently, enter in the gel water-bath of 77 DEG C, there is non-solvent and exchange heat, cause being separated.Swap time is 15 seconds, obtains primary filament film;
5) primary filament film is immersed after carrying out rinsing desolventizing in the water of 60 DEG C, in the feeder of 50 DEG C, collect and obtain polyvinylidene fluoride microporous film.
The polyvinylidene fluoride microporous film that the technology of preparing of the polyvinylidene fluoride microporous film according to said method prepares: film-strength: 6.8MPa, membrane aperture: 36nm, pure water membrane flux: 620Lm
-2h
-1, chemical-resistance: 5000ppm clorox+2wt% NaOH 15 days after-drawing intensity keeps 87%.
Comparative example 1:
1) 27 parts of polyvinylidene fluoride resins identical with embodiment 1 and 13 parts of PEG6000 are dissolved in 60 parts of dimethylacetamide solvents in 70 DEG C, make casting solution.
2) be that the dimethylacetamide amine aqueous solution of 38wt% is extruded together with casting solution as core liquid from double-deck spinning nozzle with mass fraction, the internal-and external diameter of double-deck spinning nozzle is 0.7/1.3mm, volatilize 0.6 second in the air section of 150mm subsequently, enter in the gel water-bath of 76 DEG C and exchange with non-solvent, swap time is 10 seconds, obtains primary filament film;
3) primary filament film is immersed after carrying out rinsing desolventizing in the water of 60 DEG C, in the feeder of 50 DEG C, collect the polyvinylidene fluoride microporous film obtaining comparative example 1.
The polyvinylidene fluoride microporous film that the technology of preparing of the polyvinylidene fluoride microporous film according to comparative example 1 prepares: film-strength: 2.8MPa, membrane aperture: 32nm, pure water membrane flux: 120Lm
-2h
-1, chemical-resistance: 5000ppm clorox+2wt% NaOH 15 days after-drawing intensity keeps 5%.
Comparative example 2:
1) 42 parts of polyvinylidene fluoride resins identical with embodiment 2 and 58 parts of gamma-butyrolactons are mixed, in 180 DEG C of mixing dissolvings, make casting solution.
2) be that the gamma-butyrolacton aqueous solution of 38wt% is extruded together with casting solution as core liquid from double-deck spinning nozzle with mass fraction, the internal-and external diameter of double-deck spinning nozzle is 0.7/1.3mm, volatilize 0.2 second in the air section of 50mm subsequently, enter cooling curing in the gamma-butyrolacton aqueous solution of the 70wt% of 25 DEG C, hardening time is 10 seconds, obtains primary filament film;
3) primary filament film is immersed after carrying out rinsing desolventizing in the water of 60 DEG C, in the feeder of 50 DEG C, collect the polyvinylidene fluoride microporous film obtaining comparative example 2.
The polyvinylidene fluoride microporous film that the technology of preparing of the polyvinylidene fluoride microporous film according to comparative example 2 prepares: film-strength: 3.8MPa, membrane aperture: 28nm, pure water membrane flux: 420Lm
-2h
-1, chemical-resistance: 5000ppm clorox+2wt% NaOH cannot measure hot strength after 15 days.
Claims (8)
1. a technology of preparing for polyvinylidene fluoride microporous film, is characterized in that, comprises the following steps:
1) be dissolved in 23 ~ 68 parts of dimethylacetylamides, dimethyl formamide or 1-METHYLPYRROLIDONE solvent by 25 ~ 45 parts of polyvinylidene fluoride resins by weight, control temperature, at 40 ~ 72 DEG C, stirs 3 ~ 5 hours, obtains initial soln;
2) in initial soln, add 2 ~ 5 parts of polyvinylpyrrolidones and 5 ~ 25 parts of polyethylene glycol by weight, control temperature, at 50 ~ 60 DEG C, stirs 5 ~ 7 hours, obtains one-level casting solution;
3) in described one-level casting solution, add 0.5 ~ 1.5 part of deionized water by weight, control temperature is at 40 ~ 60 DEG C, and stir 5 ~ 7 hours, standing and defoaming 10 ~ 14 hours, obtains secondary casting solution;
4) extrude from spinning nozzle together with secondary casting solution using dimethylacetamide amine aqueous solution as core liquid, after volatilizing in atmosphere 0.1 ~ 2 second, enter in the gel water-bath of more than 75 DEG C and exchange with non-solvent, swap time is 10 seconds to 20 seconds, obtains primary filament film;
5) after primary filament film is immersed in the water carries out rinsing desolventizing, in feeder, collect and obtain polyvinylidene fluoride microporous film.
2. the technology of preparing of a kind of polyvinylidene fluoride microporous film according to claim 1, is characterized in that, described step 2) in molecular weight polyethylene glycol be 20000 ~ 50000.
3. the technology of preparing of a kind of polyvinylidene fluoride microporous film according to claim 2, is characterized in that, described step 2) in polyvinylpyrrolidone be PVP-K17.
4. the technology of preparing of a kind of polyvinylidene fluoride microporous film according to claim 3, is characterized in that, in dimethylacetamide amine aqueous solution described in described step 4), the mass fraction of dimethylacetylamide is 20 ~ 38wt%.
5. the technology of preparing of a kind of polyvinylidene fluoride microporous film according to claim 4, is characterized in that, spinning nozzle described in described step 4) is double-deck spinning nozzle, and its internal-and external diameter is 0.7-0.9/1.3-1.5mm.
6. the technology of preparing of a kind of polyvinylidene fluoride microporous film according to claim 5, is characterized in that, in described step 4), non-solvent is reverse osmosis water (RO water).
7. the technology of preparing of a kind of polyvinylidene fluoride microporous film according to claim 6, is characterized in that, in described step 5), rinse temperature is 60 DEG C, and collecting temperature is 50 DEG C.
8. the polyvinylidene fluoride microporous film that the technology of preparing of the polyvinylidene fluoride microporous film according to any one of claim 1-7 prepares, is characterized in that: the film-strength 6-8MPa of polyvinylidene fluoride microporous film; Membrane aperture 20-80nm; Membrane flux >=500LMH.
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