CN101362057A - Method for preparing polyvinylidene fluoride porous membrane - Google Patents
Method for preparing polyvinylidene fluoride porous membrane Download PDFInfo
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- CN101362057A CN101362057A CNA2008101474917A CN200810147491A CN101362057A CN 101362057 A CN101362057 A CN 101362057A CN A2008101474917 A CNA2008101474917 A CN A2008101474917A CN 200810147491 A CN200810147491 A CN 200810147491A CN 101362057 A CN101362057 A CN 101362057A
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- kynoar
- solvent
- membrane
- polyvinylidene fluoride
- 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
- B01D67/002—Organic membrane manufacture from melts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
Abstract
The invention discloses a method for preparing a polyvinylidene fluoride porous membrane and relates to a method which makes use of a thermally induced phase separation method to prepare the polyvinylidene fluoride porous membrane. The method comprises the following steps: polyvinylidene fluoride with the weight percentage of 30wt-60wt and diphenyl carbonate with weight percentage of 70wt to 40wt or a composite thinner containing diphenyl carbonate with weight percentage of 70wt to 40wt are added into a high temperature resistant container, heated, rested and defoamed to prepare a polymer homogeneous film-casting solution; the film-casting solution is directly coated on a flat membrane formed by supporting network or spinned into hollow fiber by a spinneret, and then the flat membrane or the hollow fiber is immersed into cooling liquid to be treated with curing and the membrane is formed; the formed membrane is put into an extractant to extract the solvent, therefore, the polyvinylidene fluoride porous membrane is obtained. The method is characterized in that: the method adopts the diphenyl carbonate or the thinner taking the diphenyl carbonate as a main component to prepare the polyvinylidene fluoride porous membrane, the section structure of which is in communicating spongy structure, and the membrane has large water flux, high strength and good toughness.
Description
Technical field
The present invention relates to a kind of method for preparing polyvinylidene fluoride porous film, particularly adopt with diphenyl carbonate or based on the diluent of diphenyl carbonate, utilize thermally induced phase separation to prepare the method for polyvinylidene fluoride porous film, belong to the polymer material science technical field.
Background technology
Characteristics such as membrane separation technique is energy-conservation with it, equipment is simple, easy to operate, pollution-free receive publicity day by day, and have become the effective technology that substitutes traditional separation method.Membrane material in the membrane separation technique relates to polymer chemistry and Polymer Physics, and the development of membrane material is crucial in a membrane separation technique aspect.
Kynoar is by being a kind of thermoplasticity hypocrystalline high polymer, is formed by vinylidene homopolymerization or vinylidene and hexafluoropropene copolymerization, and its strand is regular to be easy to crystallization.Kynoar has outstanding anti-solvent, resistance to oxidation, uvioresistant, characteristic such as ageing-resistant and weather-proof, and it is high temperature resistant, chemical property is stable, it is the membrane material of putative excellence, the eighties so far, the patent application of preparation micro-filtration, milipore filter is constantly arranged, and these patents overwhelming majority is dull and stereotyped homogeneous membrane, composite membrane or the hollow-fibre membrane by the preparation of non-solvent precipitate gel phase inversion.The solvent that adopts mainly is N, dinethylformamide or N, N-dimethylacetylamide.But the pore-size distribution of the film that this method makes is wide and intensity is relatively poor.Thermally induced phase separation (TIPS) method is the new method of the preparation perforated membrane that rises the eighties in 20th century, and the principle of main, low temperature phase-splitting compatible with diluent high temperature by polymer causes polymer and diluent to be separated by cooling, the formation pore structure.Adopt perforated membrane, porosity height, even aperture distribution and the intensity height of the preparation of TIPS method.
The TIPS legal system is equipped with polyvinylidene fluoride porous film, normally used solvent has phthalate such as repefral or diethyl phthalate etc., cyclohexanone, 1,4-butyrolactone etc., but use above-mentioned solvent that a general shortcoming is arranged, pore structure in the polyvinylidene fluoride film is inhomogeneous, present loose spherolite packed structures, a lot of macroscopic-void defectives is arranged, the serviceability of film and mechanical strength are all not satisfactory.U.S.Pat.No.5022990 and 6299773, in order to improve loose chondritic in the film in this system blending the inorganic particulate of 20wt%～30wt% (as hydrophobic silica), by inorganic particulate pore-creating, suppressed the formation in heterogeneity cavity between chondritic, improved the transparent performance of film to a certain extent, but reduced film strength so again, also in film-forming process, must increase the process of removing inorganic particulate, increased cost.The open a kind of polyvinylidene fluoride porous film and preparation method thereof of (CN1792420) of Chinese patent, it is solvent that this method adopts benzophenone, when low copolymer concentration, obtained the spongy section structure of desirable homogeneous, but (polymer quality percentage is 30wt.%～40wt.%) in the concentration range of the polymer solution that membrane separation technique usually adopts, the prepared perforated membrane section of this method is block close-packed structure, thereby has influenced the application of polyvinylidene fluoride porous film in membrane separation technique.
Summary of the invention
The object of the present invention is to provide a kind of TIPS legal system to be equipped with the method for vinylidene perforated membrane, a kind of preparation method who under higher polymer concentration, still keeps the polyvinylidene fluoride porous film of the spongelike structure that homogeneous connects.
The preparation method of polyvinylidene fluoride porous film of the present invention carries out according to following steps:
1) polyvinylidene fluoride resin is mixed mutually with diluent; Wherein the mass percent of Kynoar is 30wt%～60wt%, and the diluent mass percent is 70wt%～40wt%;
2) mixture in the step 1) is put into the high-temperature stirring still, be warming up to 160 ℃～220 ℃, form the polymer homogeneous phase solution, standing and defoaming;
3) with step 2) in the direct blade coating of polymer homogeneous phase solution form flat sheet membrane or be spun into hollow-fibre membrane at supporting network by spinning head, then the flat sheet membrane that obtains or hollow-fibre membrane are immersed in the cooling fluid and cool off, make the solution that forms film be separated the final curing film forming;
4) extract diluent in the step 3) gained film with alcohol or ether extractant, obtain Kynoar porous flat plate film or Kynoar porous hollow fiber membrane.
The described Kynoar of step 1) is that weight average molecular weight is the Kynoar that one or more weight average molecular weight in 50,000 to 800,000 are mixed.
The described diluent of step 1) is the Kynoar high-temperature solvent, perhaps be Kynoar high-temperature solvent and Kynoar non-solvent, or Kynoar high-temperature solvent and additive, or the mixture of Kynoar high-temperature solvent, Kynoar non-solvent and additive, wherein: the high-temperature solvent mass percent is 80wt%～100wt% in the mixture, the non-solvent mass percent is 0wt%～15wt%, additive mass percent 0wt%～5wt%.
Above-mentioned high-temperature solvent is a diphenyl carbonate for the Kynoar high-temperature solvent, or one or more the double solvents of mixing in diphenyl carbonate and methyl benzoate, ethyl benzoate, glyceryl triacetate, benzophenone, diethylene glycol ether acetic acid esters, gaultherolin, diethylene glycol ether, triethyl citrate, 1,2-propylene glycol carbonate, acetophenone, cyclohexanone, r-butyrolactone, methyl isoamyl ketone, caprolactam and the phthalate; Wherein, the mass percent of diphenyl carbonate is 10wt%～90wt% in the double solvents, preferred 30wt%～70wt%.
Above-mentioned phthalate is selected from one or more the mixture in repefral, diethyl phthalate, dibutyl phthalate, diamyl phthalate, di-n-octyl phthalate, diisooctyl phthalate and phthalic acid two different thousand esters.
Described non-solvent is 1-octanol, 1-nonyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-lauryl alcohol, 1, the mixture of one or more of 2-propane diols, 1,3-propane diols, glycerine, phenmethylol, sorbierite, sweet mellow wine, diglycol, triethylene-glycol, tetraethylene-glycol, 2-hydroxyl-2-phenyl acetophenone.
It is 200～10 that described additive is selected from molecular weight, 000 polyethylene glycol, molecular weight is 10,000-100,000 PVP, polyvinyl butyral resin, neopelex, dodecyl sodium sulfate, lauryl sodium sulfate, the sorbitan fatty acid ester class nonionic emulsifier of sapn series, the polyoxyethylene sorbitan fatty acid ester nonionic emulsifier of tween series, the APES class nonionic emulsifier of OP series, ammonium chloride, lithium chloride, calcium chloride, aluminium chloride, silica, titanium dioxide, one or more mixture in calcium carbonate or the barium sulfate.
The sorbitan fatty acid ester class nonionic emulsifier of above-mentioned sapn series is span 20, span 40, sorbester p18, sorbester p38, sorbester p17 or sorbester p37; The polyoxyethylene sorbitan fatty acid ester nonionic emulsifier of tween series is polysorbas20, polysorbate40, polysorbate60, Tween 80 or polysorbate85; The APES class nonionic emulsifier of OP series is OP-4, OP-6, OP-7, OP-9 or OP-10.
The described cooling fluid of step 3) is the non-solvent of PVDF, and the temperature of described cooling fluid is 0～130 ℃.
Above-mentioned non-solvent is 1-octanol, 1-nonyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-lauryl alcohol, 1, the mixture of one or more of 2-propane diols, 1,3-propane diols, glycerine, phenmethylol, sorbierite, sweet mellow wine, diglycol, triethylene-glycol, tetraethylene-glycol and 2-hydroxyl-2-phenyl acetophenone.
The described pure kind of extractants of step 4) is methyl alcohol, ethanol, propyl alcohol, n-butanol, isobutanol or ethylene glycol; Described ether extration agent is methyl ether, ether, divinyl ether, butyl oxide or di-n-propyl ether etc.
The present invention compares with immediate prior art, has following substantial effect and conspicuousness progress:
1. the present invention adopts a kind of new high-temperature solvent---diphenyl carbonate, is equipped with polyvinylidene fluoride porous film by the TIPS legal system.Adopt method of the present invention, increased the high polymer concentration (drawing together wide) that obtains the desirable spongy membrane pore structure of homogeneous greatly to 60wt% from polymer quality specific concentration 30wt%, prepared perforated membrane section is the spongelike structure that homogeneous connects, porosity height, penetrability are good, the water permeability of film is good, the mechanical strength height; 2. the flash-point height (168 ℃) of the diphenyl carbonate that adopts of the present invention, in the film-forming process volatilization little, and can serve as the plasticizer of Kynoar, improve the extensibility and the toughness of polyvinylidene fluoride porous film, thereby improve perforated membrane elongation at break and impact strength; 3. utilize the cheap high-temperature solvent of diphenyl carbonate and other to mix mutually, can obtain the spongy membrane pore structure of desirable homogeneous equally, in the water flux and intensity that ensure film, reduced production cost; The adding of 4. a small amount of non-solvent can effectively reduce the outer surface cortex of perforated membrane under than concentration condition with higher in the Kynoar quality, has guaranteed the high water flux of film.
Description of drawings
Fig. 1, Fig. 2 are respectively film section and surface texture in the embodiment of the invention 1.
Fig. 3, Fig. 4 are respectively film section and surface texture in the embodiment of the invention 2.
Fig. 5, Fig. 6 are respectively film section structure and surface texture in the embodiment of the invention 3.
Fig. 7, Fig. 8 are respectively film section structure and surface texture in the embodiment of the invention 4.
Fig. 9, Figure 10 are respectively film section structure and surface texture in the embodiment of the invention 5.
Figure 11, Figure 12 are respectively film section structure and outer surface structure in the embodiment of the invention 5.
Figure 13, Figure 14 are respectively film section structure and surface texture in the comparative example 1 of the present invention.
The specific embodiment
The preparation method of polyvinylidene fluoride porous film of the present invention carries out according to following steps:
1) polyvinylidene fluoride resin is mixed mutually with diluent; Wherein the mass percent of Kynoar is 30wt%～60wt%, and the diluent mass percent is 70wt%～40wt%;
2) mixture in the step 1) is put into the high-temperature stirring still, be warming up to 160 ℃～220 ℃, form the polymer homogeneous phase solution, standing and defoaming;
3) with step 2) in the direct blade coating of polymer homogeneous phase solution form flat sheet membrane or be spun into hollow-fibre membrane at supporting network by spinning head, then the flat sheet membrane that obtains or hollow-fibre membrane are immersed in the cooling fluid and cool off, make the solution that forms film be separated the final curing film forming;
4) extract diluent in the step 3) gained film with alcohol or ether extractant, obtain Kynoar porous flat plate film or Kynoar porous hollow fiber membrane.
The described Kynoar of step 1) is that weight average molecular weight is the Kynoar that one or more weight average molecular weight in 50,000 to 800,000 are mixed.
The described diluent of step 1) is the Kynoar high-temperature solvent, perhaps be Kynoar high-temperature solvent and Kynoar non-solvent, or Kynoar high-temperature solvent and additive, or the mixture of Kynoar high-temperature solvent, Kynoar non-solvent and additive, wherein: the high-temperature solvent mass percent is 80wt%～100wt%, the non-solvent mass percent is 0wt%～15wt%, additive mass percent 0wt%～5wt%.
Above-mentioned high-temperature solvent is a diphenyl carbonate for the Kynoar high-temperature solvent, or one or more the double solvents of mixing in diphenyl carbonate and methyl benzoate, ethyl benzoate, glyceryl triacetate, benzophenone, diethylene glycol ether acetic acid esters, gaultherolin, diethylene glycol ether, triethyl citrate, 1,2-propylene glycol carbonate, acetophenone, cyclohexanone, r-butyrolactone, methyl isoamyl ketone, caprolactam and the phthalate; Wherein, the mass percent of diphenyl carbonate is 10wt%～90wt% in the double solvents, preferred 30wt%～70wt%.
Above-mentioned phthalate is selected from one or more the mixture in repefral, diethyl phthalate, dibutyl phthalate, diamyl phthalate, di-n-octyl phthalate, diisooctyl phthalate and the diisononyl phthalate.
Described non-solvent is 1-octanol, 1-nonyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-lauryl alcohol, 1, the mixture of one or more of 2-propane diols, 1,3-propane diols, glycerine, phenmethylol, sorbierite, sweet mellow wine, diglycol, triethylene-glycol, tetraethylene-glycol, 2-hydroxyl-2-phenyl acetophenone.
It is 200～10 that described additive is selected from molecular weight, 000 polyethylene glycol, molecular weight is 10,000-100,000 PVP, polyvinyl butyral resin, neopelex, dodecyl sodium sulfate, lauryl sodium sulfate, the sorbitan fatty acid ester class nonionic emulsifier of sapn series, the polyoxyethylene sorbitan fatty acid ester nonionic emulsifier of tween series, the APES class nonionic emulsifier of OP series, ammonium chloride, lithium chloride, calcium chloride, aluminium chloride, silica, titanium dioxide, one or more mixture in calcium carbonate or the barium sulfate.
The sorbitan fatty acid ester class nonionic emulsifier of above-mentioned sapn series is span 20, span 40, sorbester p18, sorbester p38, sorbester p17 or sorbester p37; The polyoxyethylene sorbitan fatty acid ester nonionic emulsifier of tween series is polysorbas20, polysorbate40, polysorbate60, Tween 80 or polysorbate85; The APES class nonionic emulsifier of OP series is OP-4, OP-6, OP-7, OP-9 or OP-10.
The described cooling fluid of step (3) is the non-solvent of PVDF, and the temperature of described cooling fluid is 0～130 ℃.
Above-mentioned non-solvent is 1-octanol, 1-nonyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-lauryl alcohol, 1, the mixture of one or more of 2-propane diols, 1,3 propane diols, glycerine, phenmethylol, sorbierite, sweet mellow wine, diglycol, triethylene-glycol, tetraethylene-glycol and 2-hydroxyl-2-phenyl acetophenone.
The described pure kind of extractants of step (4) is methyl alcohol, ethanol, propyl alcohol, n-butanol, isobutanol or ethylene glycol; Described ether extration agent is methyl ether, ether, divinyl ether, butyl oxide or di-n-propyl ether etc.
Below in conjunction with embodiment technical scheme of the present invention is described further, but described embodiment is not construed as limiting the invention for example.
Embodiment 1
With weight average molecular weight is 370,000 polyvinylidene fluoride resin and diphenyl carbonate, its component is that the quality percentage composition of polyvinylidene fluoride resin is 30wt%, diphenyl carbonate quality percentage composition is 70wt%, put into high-temperature stirring still heat temperature raising to 220 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 30 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is water-bath.Flat sheet membrane after the curing is dry behind ethanol extraction.
The film section is the spongelike structure that homogeneous connects, and the top layer does not have obvious cortex construction, and the fenestra aperture is about 0.8 μ m, and porosity is 76%, fracture strength 5.5MPa, elongation at break 30%, pure water flux 2,597 L/ (m
2.hr.0.1MPa).
Embodiment 2
With weight average molecular weight is 800,000 polyvinylidene fluoride resin and diphenyl carbonate, its component is that the quality percentage composition of polyvinylidene fluoride resin is 40wt%, diphenyl carbonate quality percentage composition is 60wt%, put into high-temperature stirring still heat temperature raising to 200 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 60 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is water-bath.Flat sheet membrane after the curing is dry behind ethanol extraction.
The film section is the spongelike structure that homogeneous connects, and the fenestra aperture is about 0.6 μ m, and porosity is 70%, fracture strength 6.7MPa, elongation at break 36%, pure water flux 1,524 L/ (m
2.hr.0.1MPa).
Embodiment 3
With weight average molecular weight is 50,000 polyvinylidene fluoride resin and diphenyl carbonate, its component is that the quality percentage composition of polyvinylidene fluoride resin is 60wt%, diphenyl carbonate quality percentage composition is 40wt%, put into high-temperature stirring still heat temperature raising to 160 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 130 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is an ethylene glycol bath.Flat sheet membrane after the curing is dry behind ethanol extraction.
The film section is the spongelike structure that homogeneous connects, and the fenestra aperture is about 0.2 μ m, and porosity is 50%, fracture strength 10.1MPa, elongation at break 41%, pure water flux 763 L/ (m
2.hr.0.1MPa).
Embodiment 4
With weight average molecular weight is 370,000 polyvinylidene fluoride resin and diphenyl carbonate and benzophenone, its component is that the quality percentage composition of polyvinylidene fluoride resin is 30wt%, diphenyl carbonate quality percentage composition is 63wt%, benzophenone quality percentage composition is 7wt%, put into high-temperature stirring still heat temperature raising to 200 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 0 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is water-bath.Flat sheet membrane after the curing is dry behind ethanol extraction.
The film section is the spongelike structure that homogeneous connects, and the top layer does not have obvious cortex construction, and the fenestra aperture is about 0.8 μ m, and porosity is 75%, fracture strength 5.3MPa, elongation at break 18%, pure water flux 2,012 L/ (m
2.hr.0.1MPa).
Embodiment 5
With weight average molecular weight is 370,000 polyvinylidene fluoride resin and diphenyl carbonate and phenmethylol, its component is that the quality percentage composition of polyvinylidene fluoride resin is 40wt%, diphenyl carbonate quality percentage composition is 51wt%, phenmethylol quality percentage composition is 9wt%, put into high-temperature stirring still heat temperature raising to 180 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 30 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is that 1,3-propane diols is bathed.Flat sheet membrane after the curing is dry behind ethanol extraction.
The film section is the spongelike structure that homogeneous connects, and the top layer does not have obvious cortex construction, and the fenestra aperture is about 0.8 μ m, and porosity is 70%, fracture strength 6.5MPa, elongation at break 35%, pure water flux 1,940L/ (m
2.hr.0.1MPa).
Embodiment 6
With weight average molecular weight is 370,000 polyvinylidene fluoride resin and diphenyl carbonate, 1,2-propane diols and silica, its component are that the quality percentage composition of polyvinylidene fluoride resin is 35wt%, and diphenyl carbonate quality percentage composition is 52wt%, 1,2 propane diols quality percentage compositions are 9.75wt%, and silica quality percentage composition is 3.25wt%, put into high-temperature stirring still heat temperature raising to 180 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the polymer homogeneous phase solution is extruded by spinneret orifice and formed the Kynoar doughnut, and be immersed in 130 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is that glycerine is bathed.Hollow-fibre membrane after the curing is dry behind ethanol extraction.
The film section is the spongelike structure that homogeneous connects, and the top layer does not have obvious cortex construction, external diameter 1.5mm, and internal diameter 0.9mm, the fenestra aperture is about 0.8 μ m, and porosity is 71%, fracture strength 6.2MPa, elongation at break 33%, pure water flux 2,312L/ (m
2.hr.0.1MPa).
Embodiment 7
With weight average molecular weight is 370,000 polyvinylidene fluoride resin and diphenyl carbonate, phenmethylol and dodecyl sodium sulfate, its component is that the quality percentage composition of polyvinylidene fluoride resin is 40wt%, diphenyl carbonate quality percentage composition is 48wt%, phenmethylol quality percentage composition is 9wt%, and dodecyl sodium sulfate quality percentage composition is 3wt%, puts into high-temperature stirring still heat temperature raising to 180 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the polymer homogeneous phase solution is extruded by spinneret orifice and formed the Kynoar doughnut, and be immersed in 0 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is water-bath.Hollow-fibre membrane after the curing is dry behind ethanol extraction.
The film section is the spongelike structure that homogeneous connects, and the top layer does not have obvious cortex construction, external diameter 1.2mm, and internal diameter 0.8mm, the fenestra aperture is about 1.0 μ m, and porosity is 70%, fracture strength 5.9MPa, elongation at break 30%, pure water flux 2,502L/ (m
2.hr.0.1MPa).
Embodiment 8
With weight average molecular weight is 500,000 polyvinylidene fluoride resin and diphenyl carbonate, neck dibatyl phithalate, phenmethylol and Tween 80, its component is that the quality percentage composition of polyvinylidene fluoride resin is 40wt%, diphenyl carbonate quality percentage composition is 4.8wt%, neck dibatyl phithalate quality percentage composition is 43.2wt%, phenmethylol quality percentage composition is 9wt%, Tween 80 quality percentage composition is 3wt%, put into high-temperature stirring still heat temperature raising to 200 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 0 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is water-bath.Flat sheet membrane after the curing is dry behind ethanol extraction.
The film section is the spongelike structure that homogeneous connects, and the top layer does not have obvious cortex construction, and the fenestra aperture is about 1.0 μ m, and porosity is 70%, fracture strength 6.1MPa, elongation at break 27%, pure water flux 2,413L/ (m
2.hr.0.1MPa).
Embodiment 9
With weight average molecular weight is 400,000 polyvinylidene fluoride resin and diphenyl carbonate, gamma-butyrolacton, 1,3-propane diols and lithium chloride, its component is that the quality percentage composition of polyvinylidene fluoride resin is 39wt%, diphenyl carbonate quality percentage composition is 40wt%, gamma-butyrolacton quality percentage composition is 15wt%, 1,3-propane diols quality percentage composition is 5wt%, lithium chloride quality percentage composition is 1wt%, put into high-temperature stirring still heat temperature raising to 200 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 0 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is water-bath.Flat sheet membrane after the curing is dry behind ethanol extraction.
It is equal that the film section is
The spongelike structure that connects, the top layer does not have obvious cortex construction, and the fenestra aperture is about 1.0 μ m, and porosity is 72%, fracture strength 5.7MPa, elongation at break 33%, pure water flux 2,783L/ (m
2.hr.0.1MPa).
Comparative example 1
With weight average molecular weight is 370,000 polyvinylidene fluoride resin and benzophenone, its component is that the quality percentage composition of polyvinylidene fluoride resin is 30wt%, benzophenone quality percentage composition is 70wt%, put into high-temperature stirring still heat temperature raising to 200 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 0 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is water-bath.Dry behind ethanol extraction then.
The film section is block close-packed structure, the top layer densification, and the fenestra aperture is less than 0.1 μ m, and porosity is 46%, fracture strength 1.8MPa, elongation at break 13%, pure water flux 521 L/ (m
2.hr.0.1MPa).
Comparative example 2
With weight average molecular weight is 370,000 polyvinylidene fluoride resin and Methyl Benzene-o-dicarboxylate, its component is that the quality percentage composition of polyvinylidene fluoride resin is 30wt%, Methyl Benzene-o-dicarboxylate quality percentage composition is 70wt%, put into high-temperature stirring still heat temperature raising to 200 ℃, mix and form the polymer homogeneous phase solution, left standstill 24 hours.Then the direct blade coating of polymer homogeneous phase solution is formed flat sheet membrane at supporting network, film thickness 200 μ m, and be immersed in 0 ℃ the cooling bath of liquid and make solution phase-splitting film-forming, the cooling bath of liquid is water-bath.Dry behind ethanol extraction then.
The film section is the spherulitic crystal structure that block size differs, the fracture strength 0.5MPa of film, elongation at break 7%, pure water flux 791L/ (m
2.hr.0.1MPa).
Claims (10)
1. method for preparing polyvinylidene fluoride porous film is characterized in that this method prepares as follows:
1) polyvinylidene fluoride resin is mixed mutually with diluent; Wherein the mass percent of Kynoar is 30wt%～60wt%, and the diluent mass percent is 70wt%～40wt%;
2) mixture in the step 1) is put into the high-temperature stirring still, be warming up to 160 ℃～220 ℃, form the polymer homogeneous phase solution, standing and defoaming;
3) with step 2) in the direct blade coating of polymer homogeneous phase solution form flat sheet membrane or be spun into hollow-fibre membrane at supporting network by spinning head, then the flat sheet membrane that obtains or hollow-fibre membrane are immersed in the cooling fluid and cool off, make the solution that forms film be separated the final curing film forming;
4) extract diluent in the step 3) gained film with alcohol or ether extractant, obtain Kynoar porous flat plate film or Kynoar porous hollow fiber membrane.
2. method according to claim 1 is characterized in that: described Kynoar is that weight average molecular weight is the Kynoar that one or more weight average molecular weight in 50,000 to 800,000 are mixed.
3. method according to claim 1, it is characterized in that: described diluent is the Kynoar high-temperature solvent, perhaps be Kynoar high-temperature solvent and Kynoar non-solvent, or Kynoar high-temperature solvent and additive, or the mixture of Kynoar high-temperature solvent, Kynoar non-solvent and additive, wherein: the high-temperature solvent mass percent is 80wt%～100wt% in the mixture, the non-solvent mass percent is 0wt%～15wt%, additive mass percent 0wt%～5wt%.
4. method according to claim 3, it is characterized in that: described Kynoar high-temperature solvent is a diphenyl carbonate, or one or more the double solvents of mixing in diphenyl carbonate and methyl benzoate, ethyl benzoate, glyceryl triacetate, benzophenone, diethylene glycol ether acetic acid esters, gaultherolin, diethylene glycol ether, triethyl citrate, 1,2-propylene glycol carbonate, acetophenone, cyclohexanone, r butyrolactone, methyl isoamyl ketone, caprolactam and the phthalate; Wherein, the mass percent of diphenyl carbonate is 10wt%～90wt% in the double solvents;
Described Kynoar non-solvent is 1 octanol, 1-nonyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-lauryl alcohol, 1, the mixture of one or more of 2-propane diols, 1,3-propane diols, glycerine, phenmethylol, sorbierite, sweet mellow wine, diglycol, triethylene-glycol, tetraethylene-glycol and 2-hydroxyl-2-phenyl acetophenone;
It is 200～20 that described Kynoar additive is selected from molecular weight, 000 polyethylene glycol, molecular weight is 10,000-100,000 PVP, polyvinyl butyral resin, neopelex, dodecyl sodium sulfate, lauryl sodium sulfate, the sorbitan fatty acid ester class nonionic emulsifier of sapn series, the polyoxyethylene sorbitan fatty acid ester nonionic emulsifier of tween series, the APES class nonionic emulsifier of OP series, ammonium chloride, lithium chloride, calcium chloride, aluminium chloride, silica, titanium dioxide, the mixture of one or more in calcium carbonate and the barium sulfate.
5. method according to claim 4 is characterized in that: the mass percent of diphenyl carbonate is 30wt%～70wt% in the double solvents.
6. method according to claim 4 is characterized in that: the sorbitan fatty acid ester class nonionic emulsifier of described sapn series is span 20, span 40, sorbester p18, sorbester p38, sorbester p17 or sorbester p37; The polyoxyethylene sorbitan fatty acid ester nonionic emulsifier of tween series is polysorbas20, polysorbate40, polysorbate60, Tween 80 or polysorbate85; The APES class nonionic emulsifier of OP series is OP-4, OP-6, OP-7, OP-9 or OP-10.
7. method according to claim 4 is characterized in that: described phthalate is selected from one or more the mixture in repefral, diethyl phthalate, n-butyl phthalate, amyl phthalate, di-n-octyl phthalate, diisooctyl phthalate and the diisononyl phthalate.
8. method according to claim 1, it is characterized in that: described cooling fluid is the non-solvent of Kynoar, described non-solvent is 1-octanol, 1-nonyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-lauryl alcohol, 1, the mixture of one or more of 2-propane diols, 1,3-propane diols, glycerine, phenmethylol, sorbierite, sweet mellow wine, diglycol, triethylene-glycol, tetraethylene-glycol and 2-hydroxyl-2-phenyl acetophenone.
9. method according to claim 1 is characterized in that: the temperature of described cooling fluid is 0～130 ℃.
10. method according to claim 1 is characterized in that: described pure kind of extractants is methyl alcohol, ethanol, propyl alcohol, n-butanol, isobutanol or ethylene glycol; Described ether extration agent is methyl ether, ether, divinyl ether, butyl oxide, di-n-propyl ether or benzinum.
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| CNA2008100571731A CN101293185A (en) | 2008-01-30 | 2008-01-30 | Method for producing polyvinylidene fluoride porous membrane |
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- 2008-08-21 CN CN2008101474917A patent/CN101362057B/en active Active
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| CN101362057B (en) | 2010-05-12 |
| WO2009097745A1 (en) | 2009-08-13 |
| CN101293185A (en) | 2008-10-29 |
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Assignee: Beijing Scinor Water Technology Co., Ltd. Assignor: Tsinghua University Contract record no.: 2010990000330 Denomination of invention: Method for producing polyvinylidene fluoride porous membrane Granted publication date: 20100512 License type: Exclusive License Open date: 20090211 Record date: 20100528 |