CN100478389C - Polyvinylidene fluoride and polyethersulfone blending membrane, production method and uses - Google Patents
Polyvinylidene fluoride and polyethersulfone blending membrane, production method and uses Download PDFInfo
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- CN100478389C CN100478389C CNB2005101107577A CN200510110757A CN100478389C CN 100478389 C CN100478389 C CN 100478389C CN B2005101107577 A CNB2005101107577 A CN B2005101107577A CN 200510110757 A CN200510110757 A CN 200510110757A CN 100478389 C CN100478389 C CN 100478389C
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Abstract
The invention relates to polyvinylidene fluoride/polyethersulfone blending membrane with manufacture method and application. Wherein, the method comprises: blending the materials, adding organic and inorganic additives, preparing casting-film liquid with solvent; making into plate membrane or spinning into hollow fiber membrane with dry-wet method to reduce membrane shrinkage greatly and increase flux obviously. This product can be used in flood filter, blood plasma separation and water treatment.
Description
Technical field
The present invention relates to polyvinylidene difluoride (PVDF) and polyethersulfone blending membrane, manufacture method and purposes.With the blend in the proper ratio of polyvinylidene difluoride (PVDF), polyethersulfone, add an amount of organic additive and inorganic additives, be mixed with film-casting liquid, make flat sheet membrane or adopt dried---hollow-fibre membrane is made in the wet-spinning moulding.This film can be applicable to aspects such as blood filtering, separating plasma, the concentrated feedback of ascites ultra-filtration and water treatment.
Background of invention
PVDF (polyvinylidene difluoride (PVDF)) is a kind of crystalline polymer, second-order transition temperature-39 ℃, and about 170 ℃ of crystalline melt point, heat decomposition temperature is more than 316 ℃, and mechanical property is good, has good shock-resistance, wear resistance, weathering resistance and chemical stability.At room temperature, PVDF is not corroded by acid, alkali, strong oxidizer and halogen, very stable to organic solvents such as aliphatic hydrocarbon, aromatic hydrocarbon, alcohols and aldehydes, in hydrochloric acid, nitric acid, sulfuric acid and rare, high alkali liquid and under up to 100 ℃ of temperature, its performance is constant substantially, and gamma ray resistant, ultraviolet radiation.Solvent resistance, thermostability and resistance to hydrolysis that polyvinylidene difluoride (PVDF) (PVDF) is had, and the chemical corrosion of anti-a lot of acid, alkali makes PVDF become a kind of good mould material.Its crystallizing field makes film have thermostability, and unformed area makes film have reasonable flexibility and perviousness.And it is applicable to dried-wet method or wet-spinning film forming, and is easily manufactured, with low cost, so polyvinylidene fluoride film has that better application is worth and Application Areas widely.But polyvinylidene fluoride film can produce a large amount of contractions in drying process, porosity and mean pore size are reduced and influences the stability and the Practical Performance of film.
Adopt polyvinylidene difluoride (PVDF) to report as existing many documents of material of preparing and patent.CN1128176A, CN1203119A, CN1579601A have introduced and have added non-solvent, tensio-active agent and polymer pore former spinning hollow-fibre membrane and adopt the way of back draft to make flux and the higher polyvinylidene difluoride (PVDF) hollow-fibre membrane of porosity; EP1009517 adopts phase inversion process to make the wetting ability or the asymmetric polyvinylidene fluoride microporous film of hydrophobicity of high porosity; CN1265048A is polyvinylidene fluoride resin and organic liquid and inorganic granular mixing, under 60 ℃ or higher temperature more than the fusing point of resin with the blend heating and melting of gained and make porous-film.Also there is not concrete data representation how to improve the anti-contracility energy of polyvinylidene fluoride film up to now.
1961, people such as Britton research concentrated ascites with ultra-filtration membrane, and will contain the proteinic concentrated solution injection of patient vein in order to control ascites rapidly.Sometimes patient's liver cirrhosis and liver cancer merge generation more, when these patients' ascites ultra-filtration is concentrated, should at first remove cancer cells and bacterium, with diffusion and the side effect that prevents cancer cells, this treatment process is known as " degerming, remove cancer cells concentrate the method for reinjecting ".This method will be used two kinds of films, a kind of cancer cells and bacterium that is used for removing in the ascites, and another kind is used for proteins concentrate.The former aperture is 0.1～0.2um, and albumen mass-energy is passed through, and cancer cells and bacterium can not pass through.The latter is a ultra-filtration membrane, and protein can not pass through, and water and other low-molecular material mass-energy are passed through.The present invention has made that shrinking percentage is lower, permeability is stable, and the aperture that can allow protein pass through is the microporous membrane of 0.1～0.2um, and this film also can be applicable to aspects such as blood filtering, separating plasma and water treatment simultaneously.
Summary of the invention:
The blend film that the purpose of this invention is to provide a kind of polyvinylidene difluoride (PVDF) and polyethersulfone, described blend film are flat sheet membrane or hollow-fibre membrane.
Purpose of the present invention also provides the preparation method of the blend film of a kind of above-mentioned polyvinylidene difluoride (PVDF) and polyethersulfone.
Another object of the present invention provides the purposes of the blend film of a kind of above-mentioned polyvinylidene difluoride (PVDF) and polyethersulfone.
Polyvinylidene difluoride (PVDF) and polyethersulfone are the non-compatibility superpolymer, and when they were dissolved in the solvent jointly or make mould material, they were not to be that unit mixes mutually with the molecule, but form separately independently the phase farmland and mix mutually.The size on phase farmland is relevant with the consistency of two kinds of polymkeric substance, and good more its phase farmland of consistency is more little, and the hole between the phase farmland is also less, and the pore size that forms after the film forming is less; Consistency difference person, the independent phase farmland in the solution is bigger, and the hole between the phase farmland is also bigger, so can form larger-size micropore after the film forming.The present invention utilizes the higher anti-contracility energy that reduces polyvinylidene fluoride film of the second-order transition temperature of polyethersulfone; Simultaneously with the relatively poor bigger blend film of micropore of making of the consistency of polyvinylidene difluoride (PVDF) and polyethersulfone to improve its transparent performance.
The blend film of polyvinylidene difluoride (PVDF) of the present invention and polyethersulfone is made up of the material of following weight ratio: 8～25 polyvinylidene difluoride (PVDF), 1～8 polyethersulfone and 1～15 pore former.Described pore former is polyvinylpyrrolidone, ethylene glycol, lithium chloride, Sodium Nitrite, water or their mixture.
Described polyvinylidene difluoride (PVDF) η=1.5～2.0, polyethersulfone η=0.4～0.55.This blend film can be flat sheet membrane or hollow-fibre membrane, especially hollow-fibre membrane.
The preparation method of the blend film of above-mentioned polyvinylidene difluoride (PVDF) of the present invention and polyethersulfone is following realization: the preparation preparation liquid prepares flat sheet membrane or adopts dried-wet method to spin the unsymmetric structure hollow-fibre membrane of having got everything ready by flat band method.
In present method, the preparation of preparation liquid is the material co-blended with the following weight ratio:
Polyvinylidene difluoride (PVDF) (η=1.5～2.0) 8～25;
Polymer blend (η=0.4～0.55) 1～8;
Pore former 1～15;
Organic solvent 70～90.
Above-mentioned pore former comprises polyvinylpyrrolidone, ethylene glycol, lithium chloride, Sodium Nitrite or water, and they may be used alone, can also be used in combination.Organic solvent is dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
Prepare burden as stated above, and the solid matter drying is removed moisture, all raw materials are put into dissolution kettle then, heating for dissolving under 60～100 ℃ of stirrings.Time is 4～6 hours, then filters, scavenging process such as deaeration.
The making processes of flat sheet membrane:
Above-mentioned preparation liquid is formed the layer of even solution layer on the flat board of cleaning, the prevapourising time is 0～100 minute, and the prevapourising medium is air (20～80 ℃ of temperature, a relative humidity 50～90%), immerses film forming in the precipitation bath then.After forming, film uses the distilled water thorough washing, with the flush away solvent.Protect the hole with the aqueous solution of 20%～60% monohydroxy-alcohol or polyvalent alcohol then and handle, this alcohols can be methyl alcohol, ethanol, propyl alcohol, ethylene glycol or glycerol etc.Protect 4～8 hours hole treatment times, last oven drying at low temperature promptly makes finished film.
Precipitation bath can be adopted water, contain the above-mentioned organic solvent of 0～50% weight or the aqueous solution of alcohols in the above-mentioned film-forming process.Described alcohols is alcohols such as methyl alcohol, ethanol, propyl alcohol, glycerol, Virahol, butanols, octanol.
The percentage reduction of area of the flat sheet membrane that aforesaid method makes is 4～4.5%, and thickness is 50～200 μ m, and mean pore size is 0.02～0.15 μ m, and pure water flux is 50～400L/m
2.h (0.1MPa), the bovine serum albumin rejection is 18～90%, proof pressure 〉=0.1MPa.
The making processes of hollow-fibre membrane:
Spinning process is that to adopt dry-jet wet spinning to be formed in the volume pump rotating speed be 8～20r/min, spinning pressure is under 0.4～0.6Mpa, the spinning nozzle that slurries are formed from two concentric tubes is extruded, after the dry-spinning path of 50～400mm, be 0～10% at solvent, temperature is to solidify in 25～60 ℃ the aqueous solution, nascent hollow-fibre membrane stretches through four roads, the washing of three roads, reels with the speed of 20～50m/min, and protects the hole processing and promptly get blend hollow fiber membrane provided by the present invention.
In the above-mentioned spinning process, spinning nozzle inner chamber filling liquid pressure is 1.5 * 10
-3MPa～5.5 * 10
-3MPa, filling liquid is 0～10% solvent aqueous solution or ethanol, glycerin solution.
In order to reduce the distortion of fenestra in drying process, must protect the hole and handle 4-8 hour, protect the hole agent and be 20～60% the monohydroxy-alcohol or the aqueous solution of polyvalent alcohol, both can use separately, also can use simultaneously.
The tubular fibre film thickness that is spun into is 50～200 μ m, and internal diameter is 200～500 μ m, and shrinking percentage is 5.5～6.5%, and pure water flux is 50～500L/m
2.h (0.1MPa), the bovine serum albumin rejection is 40～90%, proof pressure 〉=0.1MPa
Adopting polyethersulfone (PES) is intermingling material, because PES has good dimensional stability and chemical stability, thereby low contraction, high-throughput have been made, hold back the blend hollow fiber membrane that relative molecular mass reduces (can regulate by regulating forming technology).
It is intermingling material that the present invention adopts polyethersulfone, adds a spot of polyethersulfone the shrinking percentage of film is declined to a great extent, and flux is largely increased, and the transparent performance of film and cutoff performance can be regulated effectively; Film strength is higher, has anti-damage performance preferably; Chemical stability is better, has long work-ing life; Anti-steam disinfection is better, and has good blood compatibility.
Embodiment
To help to understand the present invention by following examples, but not limit content of the present invention.
Embodiment 1
Prepare burden by following component and composition: PVDF 13.5%; PES 1.5%; PVP 5%; DMAc 80%.Above-mentioned raw materials is added in the dissolver, under the control of 40～80 ℃ of temperature, makes film-casting liquid through swelling and dissolving, film-casting liquid after filtration, stand-by after the deaeration.The clean sheet glass and the temperature of scraper and film-casting liquid are consistent, film-casting liquid is poured on an end of sheet glass, make it form the layer of even liquid film with scraper, behind the prevapourising 30 seconds, be immersed in the water-bath, when nascent film from the sheet glass floating come up after, with the distilled water thorough washing, soak with the flush away solvent, oven drying at low temperature after protecting the hole and handling.Percentage reduction of area before and after this film oven dry is 4.4%, and water flux is 350L/m
2.h, the rejection of bovine serum albumin is 20%.This film can be applicable to separating plasma, the spissated preceding road of ascites ultra-filtration filters and the water treatment aspect
Embodiment 2
Film-casting liquid among the embodiment 1 is spun into hollow-fibre membrane through concentric(al) circles tubular type spinning nozzle, and film-forming process is: volume pump specification 0.35ml/r, and revolution speed 11r/min, air section length 180mm, inside and outside precipitation bath is a water, spinning speed 28m/min.Cryodrying can be assembled after handle in washing, guarantor hole.Length shrinking percentage before and after this film drying is 6.5%, and water flux is 500L/m
2.h, the rejection of bovine serum albumin is 38%.This film can be applicable to separating plasma, ascites ultra-filtration concentrates the preceding road that feeds back and filters and the water treatment aspect
Comparative example 1
Prepare burden by following component and composition: PVDF 15%; PVP 5%; DMAc 80%.Above-mentioned raw materials is pressed the method dissolving of embodiment 1 and made film, the percentage reduction of area before and after this film oven dry is 7.4%, and water flux is 210L/m
2.h, the rejection of bovine serum albumin is 37%.
Comparative example 2
Film-casting liquid among the embodiment 1 is spun into hollow-fibre membrane through concentric(al) circles tubular type spinning nozzle, and film-forming process is undertaken by the method for embodiment 2.Length shrinking percentage before and after this film drying is 15.6%, and water flux is 37L/m
2.h, the rejection of bovine serum albumin is 81%.
Claims (3)
1. the blend hollow fiber membrane of polyvinylidene difluoride (PVDF) and polyethersulfone is characterized in that described hollow-fibre membrane is made up of the material of following weight ratio: 8～25 polyvinylidene difluoride (PVDF), 1～8 polyethersulfone and 1～15 pore former; Described pore former is polyvinylpyrrolidone, ethylene glycol, lithium chloride, Sodium Nitrite, water or their mixture; Described polyvinylidene difluoride (PVDF) η=1.5～2.0, polyethersulfone η=0.4～0.55; The tubular fibre film thickness is 50～200 μ m, and internal diameter is 200～500 μ m, and shrinking percentage is 5.5～6.5%, and pure water flux is 50～500L/m under 0.1MPa
2.h, the bovine serum albumin rejection is 40～90%, proof pressure 〉=0.1MPa.
2. the making method of a polyvinylidene blending hollow-fibre membrane as claimed in claim 1 is characterized in that making by the method for following (1) and (2):
(1), join preparation liquid:
Material co-blended with the following weight ratio:
The polyvinylidene difluoride (PVDF) 8～25 of η=1.5～2.0;
The polyethersulfone 1～8 of η=0.4～0.55;
Pore former 1～15;
Organic solvent 70～90;
(2), adopt dried-wet method spinning to be equipped with hollow-fibre membrane:
The film liquid of (1) is entered concentric(al) circles tubular type spinning nozzle after the volume pump metering clamp-on in the air, enter solvent after after the dry-spinning path of 50～400mm and be 0～10%, temperature is to solidify in 25～60 ℃ the aqueous solution, form nascent film, nascent film stretches through four roads, the washing of three roads, speed with 20～50m/min is reeled, and protects and makes hollow-fibre membrane after the hole is handled and dried; Wherein, spinning nozzle inner chamber filling liquid pressure is 1.5 * 10
-3MPa～5.5 * 10
-3MPa, filling liquid is 0～10% the ethanol or the aqueous solution of glycerol;
Handle in described guarantor hole is that the monohydroxy-alcohol of employing 20%～60% or the aqueous solution of polyvalent alcohol are protected hole processing 4～8 hours; Described pore former according to claim 1; Described organic solvent is dimethyl sulfoxide (DMSO), dimethyl formamide, N,N-DIMETHYLACETAMIDE or N-Methyl pyrrolidone.
3. making method according to claim 2 is characterized in that the metering revolution speed is 8～20r/min in the described method (2), and spinning pressure is 0.4～0.6Mpa.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2005101107577A CN100478389C (en) | 2005-11-25 | 2005-11-25 | Polyvinylidene fluoride and polyethersulfone blending membrane, production method and uses |
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| CNB2005101107577A CN100478389C (en) | 2005-11-25 | 2005-11-25 | Polyvinylidene fluoride and polyethersulfone blending membrane, production method and uses |
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| CN100478389C true CN100478389C (en) | 2009-04-15 |
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Families Citing this family (15)
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| CN100366666C (en) * | 2006-05-11 | 2008-02-06 | 复旦大学 | Method for hydrophilic modifying of poly-vinylidene fluoride film |
| CN100417434C (en) * | 2006-05-19 | 2008-09-10 | 广州美能材料科技有限公司 | Process for preparing composite hollow fiber membrane |
| CN101269302B (en) * | 2008-05-06 | 2011-08-31 | 南京奥特高科技有限公司 | Non-crystallization permanent hydrophilic PVDF membrane material and preparation method thereof |
| CN101422706B (en) * | 2008-11-18 | 2011-07-20 | 东华大学 | Preparation method of co-mixing polyvinylidene fluoride hollow fiber membrane with improved hydrophilicity |
| CN101485961B (en) * | 2009-01-08 | 2013-01-30 | 杭州水处理技术研究开发中心有限公司 | Method for preparing polyvinylidene fluoride hollow fiber alloy film |
| CN101733022B (en) * | 2009-03-12 | 2013-01-23 | 北京碧水源膜科技有限公司 | High-strength polyvinylidene fluoride hollow fiber membrane and production method thereof |
| CN102219969B (en) * | 2010-04-13 | 2013-06-19 | 广州美能材料科技有限公司 | Polyvinylidene fluoride-polyether sulfone blended hollow fiber membrane and thermally induced phase separation preparation method |
| CN102228804A (en) * | 2011-04-15 | 2011-11-02 | 天津科技大学 | Method for preparing hydrophobic microporous membrane and membrane prepared by method |
| CN102861519B (en) * | 2011-07-05 | 2016-06-01 | 北京金通量科技有限公司 | The preparation method of long-acting hydrophilic polyvinyl chloride hollow fiber ultrafiltration membrane |
| CN103406032B (en) * | 2013-07-26 | 2015-12-02 | 东华大学 | A kind of polyvinyl chloride/sulfonated polyethersulfone blending membrane and preparation method thereof |
| CN103920398B (en) * | 2014-04-25 | 2017-06-16 | 天津工业大学 | A kind of hollow-fibre membrane and preparation method thereof |
| EP3311857B1 (en) | 2015-06-17 | 2024-04-10 | Asahi Kasei Medical Co., Ltd. | Blood-processing filter |
| CN107591545A (en) * | 2016-07-07 | 2018-01-16 | 中国科学院大连化学物理研究所 | A kind of application of blended porous membrane in flow battery |
| CN108786486A (en) * | 2018-07-02 | 2018-11-13 | 上海城市水资源开发利用国家工程中心有限公司 | A kind of coating Raolical polymerizable method preparation PES/PVDF function ultrafiltration film methods |
| CN111644074B (en) * | 2020-07-17 | 2022-12-30 | 安徽森诺膜技术有限公司 | Polyvinylidene fluoride hollow fiber membrane and preparation method thereof |
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