CN101703896A - Polyvinylidene fluoride microporous filtering film with high flux and preparation method thereof - Google Patents
Polyvinylidene fluoride microporous filtering film with high flux and preparation method thereof Download PDFInfo
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- CN101703896A CN101703896A CN200910228926A CN200910228926A CN101703896A CN 101703896 A CN101703896 A CN 101703896A CN 200910228926 A CN200910228926 A CN 200910228926A CN 200910228926 A CN200910228926 A CN 200910228926A CN 101703896 A CN101703896 A CN 101703896A
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Abstract
The invention relates to a polyvinylidene fluoride microporous filtering film with high flux and a preparation method thereof. Polyvinylidene fluoride is used as a material and is prepared into a casting solution with polar organic solvents through freezing. The molecular weight of the olyvinylidene fluoride is 1 to one hundred thousand. The pore diameter of the microporous filtering film is 1 to 5 micrometers, the thickness is 100 to 300 micrometers, the water flux is 130 to 1500 L/m2h under 50 kPa, and the water flux is 250 to 2g00L/m2h under 100 kPa. The preparation method comprises the following steps of dissolving the polyvinylidene fluoride film material in the polar organic solvents, stirring the mixture in water bath with the temperature of 60 DEG C to prepare a homogeneous casting solution , standing for deaeration, pouring the casting solution on a glass plate for knifing, then placing in a refrigerator for freezing, and washing with water to obtain the PVDF microporous filtering film. The polyvinylidene fluoride microporous filtering film has high flux and high mechanical strength, and the preparation method has simple process, mild condition and can be applied to the fields of biological separation, water treatment, air purification, and the like.
Description
Technical field
The present invention relates to a kind of high-throughout polyvinylidene fluoride microporous filtering film and preparation method thereof, be specially the method that a kind of freezing prepares polyvinylidene fluoride microporous filtering film.
Background technology
Micro-filtration is a kind of important film separation process, in fields such as bio-separation, water treatment, air cleanings important application is arranged.The aperture of micro-filtration membrane is generally 0.1～10 micron, between conventional filtration and ultrafiltration.According to screening mechanism, particle diameter is trapped greater than the particle in micro-filtration membrane aperture, and granule sees through micro-filtration membrane.From the 1950's so far, world's micro-filtration membrane technology has obtained rapidly development, range of application enlarges gradually.At present obtained using widely in fields such as the filtration of the aseptic filtration of end-filtration, mineral water and the pure water of industrial pure water, ultrafiltration water, infusion solutions water and household water filters.
Kynoar (PVDF) belongs to crystalline polymer, has the mechanical strength height, and radioresistance is good, the good characteristics such as (acid and alkali-resistance, strong oxidizer and halogens etc.) of chemical stability.PVDF can only be dissolved in strong polar organic solvent usually, as: N, dinethylformamide, N, N-dimethylacetylamide and dimethyl sulfoxide (DMSO) etc.Based on its good physical and chemical performance, PVDF is one of the most frequently used material of preparation micro-filtration membrane.PVDF micro-filtration membrane novel and high-efficiency controllable preparation method is the problem that is worth everybody to pay close attention to always.
The preparation of PVDF micro-filtration membrane adopts non-solvent to induce phase inversion (DIPS) and thermally induced phase separation (TIPS) more.It is that development is compared early that non-solvent is induced phase inversion, the technology mature methods, and this method is fairly simple comparatively speaking, and then mechanical strength is very poor as not adding backing material in addition for the film that DIPS makes; Porosity is low, and some material does not almost have flux as the film that not doping then makes; And often need in coagulation bath, add multiple non-solvent, cause prescription complicated.Thermally induced phase separation is to utilize crystallinity and thermoplastic polymer and higher boiling, low-molecular-weight diluent to form the homogeneous phase casting solution when high temperature, and solid-liquid or liquid-liquid phase separation take place when temperature reduces, and removes diluent afterwards, obtains polymer microporous film.The film that TIPS makes has improved the mechanical strength of film to a certain extent, but required film forming condition is relatively harsher, the binary mixture that often needs polymer and diluent (single or composite thinning agent), high temperature (solution temperature that is higher than polymer far away) and a large amount of extractants cause the waste of energy and reagent.
Be frozen into that embrane method mainly is based on the reduction of the solubility with temperature of high molecular polymer in solvent and the principle that descends, drive and cause high molecular separating out and film forming by the reduction of temperature.This kind film-forming method is simple; Do not need non-solvent and extractant, save medicine, and do not need high temperature, save the energy; The film mechanical strength height that makes, flux is big.In sum, be frozen into embrane method and have many advantages.
Summary of the invention
The object of the present invention is to provide a kind of high-throughout polyvinylidene fluoride microporous filtering film and preparation method thereof, this procedure is simple, and with the PVDF micro-filtration membrane of the method preparation, pure water flux significantly improves, and mechanical strength significantly strengthens.
A kind of high-throughout polyvinylidene fluoride microporous filtering film provided by the invention is to be that raw material is mixed with casting solution through cryopreparation with Kynoar and strong polar organic solvent, and the mass concentration of described Kynoar in strong polar organic solvent is 20%～40%; Heating is mixed with casting solution to concrete preparation process in the strong polar organic solvent in order Kynoar is dissolved in, deaeration, and casting solution is poured over glass plate, scrapes to make the nascent state film; Described micro-filtration membrane aperture is the 1-5 micron, and thickness is the 100-300 micron, and water flux is 130～1500L/m under 50kPa
2H, 250～2800L/m under 100kPa
2H.
The molecular weight of described Kynoar is 1-10 ten thousand.
A kind of high-throughout polyvinylidene fluoride microporous filtering film preparation method provided by the invention may further comprise the steps:
1) Kynoar is dissolved in the strong polar organic solvent, 60 ℃ stirred in water bath 4-5 hour to evenly, be mixed with the homogeneous phase casting solution;
2) casting solution left standstill 5-6 hour, deaeration, and after bubble removed, casting solution was poured over glass plate, scraped and made the nascent state film;
3) the nascent state film with striking places refrigerator and cooled to freeze, and forms solid film;
4) solid film is taken off from glass plate, water fully washes immersion, removes organic solvent, obtains polyvinylidene fluoride microporous filtering film.
Described strong polar organic solvent is N, dinethylformamide, N, N-dimethylacetylamide and dimethyl sulfoxide (DMSO) or their mixed liquor.
Described cryogenic temperature be 4 to subzero 10 the degree, cooling time is 15 to 120 minutes.
The present invention is based on the decline of the solubility with temperature of high polymer in solvent and the principle that reduces, and polymer gelization forms solid-state perforated membrane.The film preparation process is simple, mild condition, and the flux of polyvinylidene fluoride film and mechanical strength height (seeing accompanying drawing 2), and have good separating property, film reaches 100% to saccharomycetic holding back.The present invention can be used for fields such as bio-separation, water treatment, air cleaning.
Description of drawings
Fig. 1 is micro-filtration membrane surface scan Electronic Speculum figure of the present invention: a:PVDF content 20%, b:PVDF content 30%, c:PVDF content 40%.
Fig. 2 is micro-filtration membrane profile scanning Electronic Speculum figure of the present invention: d:PVDF content 20%, e:PVDF content 30%, f:PVDF content 40%.
The specific embodiment
Embodiment 1
Take by weighing 4.0g PVDF and 16.0g solvent dimethyl sulfoxide (DMSO) is put into there-necked flask, place stirring and dissolving 4～5h under 60 ℃ of water-bath 900r/min rotating speeds, form transparent limpid homogeneous phase casting solution; After stirring casting solution is left standstill 5h under 60 ℃, remove the bubble in the casting solution; Get clean simple glass plate, self-control scraper, lie against on the desktop, after cleaning with absolute ethyl alcohol, from water bath with thermostatic control, take out casting solution, an amount of casting solution is poured into glass plate one end, and at the uniform velocity the horizontal drawing scraper scrapes the thick nascent state film of about 240 μ m to the glass plate other end on glass plate; After the striking of nascent state film, put into refrigerator frozen coating (10 ℃), obtain the PVDF solid film, fully wash with distilled water then, obtain the PVDF micro-filtration membrane.Prepared PVDF micro-filtration membrane is through scanning electron microscope analysis, and film pore-forming performance is good, and fenestra is evenly distributed.The pure water flux of PVDF micro-filtration membrane reaches 1114.9L/m
2H (under the 50kPa), and the pvdf membrane that phase inversion makes does not almost have flux.Measure in the microfiltration process through saccharomycetic concentration (530nm) in liquid and the trapped fluid by ultraviolet-visible spectrophotometer.The film of this law preparation reaches 100% to saccharomycetic holding back.
Embodiment 2
Take by weighing 5.0g PVDF and 15.0g solvent dimethyl sulfoxide (DMSO) is put into there-necked flask, place stirring and dissolving 5h under 60 ℃ of water-bath 900r/min rotating speeds, form transparent limpid homogeneous phase casting solution; After stirring casting solution is left standstill 6h under 60 ℃, remove the bubble in the casting solution; Get clean simple glass plate, self-control scraper, lie against on the desktop, after cleaning with absolute ethyl alcohol, from water bath with thermostatic control, take out casting solution, an amount of casting solution is poured into glass plate one end, and at the uniform velocity the horizontal drawing scraper scrapes the thick nascent state film of about 240 μ m to the glass plate other end on glass plate; After the striking of nascent state film, put into refrigerator frozen coating (10 ℃) again, obtain the PVDF solid film, fully wash with distilled water then, obtaining the PVDF micro-filtration membrane. prepared PVDF micro-filtration membrane is through scanning electron microscope analysis, film pore-forming performance is good, and the be evenly distributed pure water flux of .PVDF micro-filtration membrane of fenestra is 737.56L/m at 50kPa
2H is 1623.5L/m at 100kPa
2H, and the pvdf membrane that phase inversion makes does not almost have flux, the film that thermally induced phase separation makes can only reach 900L/m under 100kPa
2H.Measure in the microfiltration process through saccharomycetic concentration (530nm) in liquid and the trapped fluid by ultraviolet-visible spectrophotometer.The film of this law preparation reaches 100% to saccharomycetic holding back.
Take by weighing 6.0g PVDF and 14.0g solvent dimethyl sulfoxide (DMSO) is put into there-necked flask, place stirring and dissolving 5.5h under 60 ℃ of water-bath 900r/min rotating speeds, form transparent limpid homogeneous phase casting solution; After stirring casting solution is left standstill 5h under 60 ℃, remove the bubble in the casting solution; Get clean simple glass plate, self-control scraper, lie against on the desktop, after cleaning with absolute ethyl alcohol, from water bath with thermostatic control, take out casting solution, an amount of casting solution is poured into glass plate one end, and at the uniform velocity the horizontal drawing scraper scrapes the thick nascent state film of about 240 μ m to the glass plate other end on glass plate; After the striking of nascent state film, in air, place and put into refrigerator frozen coating (10 ℃) after 10～30 seconds again, obtain the PVDF solid film, fully wash with distilled water then, obtain the PVDF micro-filtration membrane at last.Prepared PVDF micro-filtration membrane is through scanning electron microscope analysis, and film pore-forming performance is good, and fenestra is evenly distributed.The pure water flux of this film is 450.5L/m under 50kPa
2H, 940.3L/m under 100kPa
2H.And the pvdf membrane that phase inversion makes does not almost have flux, and the film that thermally induced phase separation makes can only reach 400L/m under 100kPa
2H.Measure in the microfiltration process through saccharomycetic concentration (530nm) in liquid and the trapped fluid by ultraviolet-visible spectrophotometer.The film of this law preparation reaches 100% to saccharomycetic holding back.
Embodiment 4
Take by weighing 7.0g PVDF and 13.0g solvent dimethyl sulfoxide (DMSO) is put into there-necked flask, place stirring and dissolving 4h under 60 ℃ of water-bath 900r/min rotating speeds, form transparent limpid homogeneous phase casting solution; After stirring casting solution is left standstill 6h under 60 ℃, remove the bubble in the casting solution; Get clean simple glass plate, self-control scraper, lie against on the desktop, after cleaning with absolute ethyl alcohol, from water bath with thermostatic control, take out casting solution, an amount of casting solution is poured into glass plate one end, and at the uniform velocity the horizontal drawing scraper scrapes the thick nascent state film of about 240 μ m to the glass plate other end on glass plate; After the striking of nascent state film, put into refrigerator frozen coating (10 ℃), obtain the PVDF solid film, fully wash with distilled water then, obtain the PVDF micro-filtration membrane at last.Prepared PVDF micro-filtration membrane is through scanning electron microscope analysis, and film pore-forming performance is good, and fenestra is evenly distributed.The pure water flux of this film is 223.69L/m under 50kPa
2H, 510.6L/m under 100kPa
2H.And the film that thermally induced phase separation makes can only reach 200L/m under 100kPa
2H.Measure in the microfiltration process through saccharomycetic concentration (530nm) in liquid and the trapped fluid by ultraviolet-visible spectrophotometer.The film of this law preparation reaches 100% to saccharomycetic holding back.
Embodiment 5
Take by weighing 8.0g PVDF and 12.0g solvent dimethyl sulfoxide (DMSO) is put into there-necked flask, place stirring and dissolving 5h under 60 ℃ of water-bath 900r/min rotating speeds, form transparent limpid homogeneous phase casting solution; After stirring casting solution is left standstill 5h under 60 ℃, remove the bubble in the casting solution; Get clean simple glass plate, self-control scraper, lie against on the desktop, after cleaning with absolute ethyl alcohol, from water bath with thermostatic control, take out casting solution, an amount of casting solution is poured on glass plate one end, and at the uniform velocity the horizontal drawing scraper scrapes the thick nascent state film of about 240 μ m to the glass plate other end on glass plate; After the striking of nascent state film, put into refrigerator frozen coating (10 ℃), obtain the PVDF solid film, fully wash with distilled water then, obtaining the PVDF micro-filtration membrane at last. prepared PVDF micro-filtration membrane is through scanning electron microscope analysis, film pore-forming performance is good, and fenestra is evenly distributed. and the pure water flux of this film is 176L/m under 50kPa
2H, 336.8L/m under 100kPa
2H.And the film that thermally induced phase separation makes can only reach 100L/m under 100kPa
2H.Measure in the microfiltration process through saccharomycetic concentration (530nm) in liquid and the trapped fluid by ultraviolet-visible spectrophotometer.The film of this law preparation reaches 100% to saccharomycetic holding back.
The mechanical performance of each film under table 1 variable concentrations
| The film numbering | Strain (%) | Deformation quantity (mm) | Young's modulus of elasticity (MPa) | Stress (MPa) |
| ??20％ | ??8.920 | ??2.676 | ??14.562 | ??0.460 |
| ??25％ | ??9.827 | ??2.948 | ??28.928 | ??0.732 |
| ??30％ | ??16.000 | ??4.800 | ??69.909 | ??1.517 |
| ??35％ | ??12.403 | ??3.721 | ??96.100 | ??2.117 |
| ??40％ | ??15.380 | ??3.214 | ??120.771 | ??2.738 |
Claims (5)
1. high-throughout polyvinylidene fluoride microporous filtering film, it is characterized in that it is is that raw material is mixed with casting solution through cryopreparation with Kynoar and strong polar organic solvent, the mass concentration of described Kynoar in strong polar organic solvent is 20%～40%; Heating is mixed with casting solution to concrete preparation process in the strong polar organic solvent in order Kynoar is dissolved in, deaeration, and casting solution is poured over glass plate, scrapes to make the nascent state film; Described micro-filtration membrane aperture is the 1-5 micron, and thickness is the 100-300 micron, and water flux is 130～1500L/m under 50kPa
2H, 250～2800L/m under 100kPa
2H.
2. polyvinylidene fluoride microporous filtering film according to claim 1, the molecular weight that it is characterized in that described Kynoar is 1-10 ten thousand.
3. the preparation method of the described polyvinylidene fluoride microporous filtering film of claim 1, its feature may further comprise the steps:
1) Kynoar is dissolved in the strong polar organic solvent, 60 ℃ stirred in water bath 4-5 hour to evenly, be mixed with the homogeneous phase casting solution;
2) casting solution left standstill 5-6 hour, deaeration, and after bubble removed, casting solution was poured over glass plate, scraped and made the nascent state film;
3) the nascent state film with striking places refrigerator and cooled to freeze, and forms solid film;
4) solid film is taken off from glass plate, water fully washes immersion, removes organic solvent, obtains polyvinylidene fluoride microporous filtering film.
4. preparation method according to claim 3 is characterized in that described strong polar organic solvent is N, dinethylformamide, N, N-dimethylacetylamide and dimethyl sulfoxide (DMSO) or their mixed liquor.
5. preparation method according to claim 3, it is characterized in that described cryogenic temperature be 4 to subzero 10 the degree, cooling time is 15 to 120 minutes.
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| CN200910228926A CN101703896A (en) | 2009-12-02 | 2009-12-02 | Polyvinylidene fluoride microporous filtering film with high flux and preparation method thereof |
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| CN200910228926A CN101703896A (en) | 2009-12-02 | 2009-12-02 | Polyvinylidene fluoride microporous filtering film with high flux and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106731900A (en) * | 2017-01-12 | 2017-05-31 | 常州大学 | In-situ sol-gel high-strength polyvinylidene fluoride milipore filter and preparation method |
| CN109569327A (en) * | 2018-12-21 | 2019-04-05 | 中国科学技术大学 | A kind of polyacrylonitrile nanofiber perforated membrane and preparation method thereof |
| CN115121133A (en) * | 2022-07-04 | 2022-09-30 | 济南大学 | PVDF film for water treatment and preparation method thereof |
| CN117123061A (en) * | 2023-10-26 | 2023-11-28 | 江苏关怀医疗科技有限公司 | Separation membrane, preparation method of separation membrane and filtering device using separation membrane |
| CN117123061B (en) * | 2023-10-26 | 2024-10-22 | 江苏关怀医疗科技有限公司 | Separation membrane, preparation method of separation membrane and filtering device using separation membrane |
-
2009
- 2009-12-02 CN CN200910228926A patent/CN101703896A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106731900A (en) * | 2017-01-12 | 2017-05-31 | 常州大学 | In-situ sol-gel high-strength polyvinylidene fluoride milipore filter and preparation method |
| CN109569327A (en) * | 2018-12-21 | 2019-04-05 | 中国科学技术大学 | A kind of polyacrylonitrile nanofiber perforated membrane and preparation method thereof |
| CN115121133A (en) * | 2022-07-04 | 2022-09-30 | 济南大学 | PVDF film for water treatment and preparation method thereof |
| CN117123061A (en) * | 2023-10-26 | 2023-11-28 | 江苏关怀医疗科技有限公司 | Separation membrane, preparation method of separation membrane and filtering device using separation membrane |
| CN117123061B (en) * | 2023-10-26 | 2024-10-22 | 江苏关怀医疗科技有限公司 | Separation membrane, preparation method of separation membrane and filtering device using separation membrane |
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Open date: 20100512 |