CN101138708A - Method for producing polyvinylidene fluoride porous membrane by using composite thinning agent - Google Patents
Method for producing polyvinylidene fluoride porous membrane by using composite thinning agent Download PDFInfo
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- CN101138708A CN101138708A CNA2006101268376A CN200610126837A CN101138708A CN 101138708 A CN101138708 A CN 101138708A CN A2006101268376 A CNA2006101268376 A CN A2006101268376A CN 200610126837 A CN200610126837 A CN 200610126837A CN 101138708 A CN101138708 A CN 101138708A
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Abstract
The present invention relates to a manufacture method of a polyvinylidene fluoride multi-pore membrane and comprises a flat membrane and a hollow fiber membrane. The manufacture method is that the polyvinylidene fluoride and a mixed solvent of a plurality of diluents are added into a dissolving tank; the content of the polyvinylidene fluoride is 20wt-40wt percent, and the content of the mixed solvent is 80wt-60wt percent; the polyvinylidene fluoride and the mixed solvent are mixed and dissolved under a high temperature to form a transparent solution, which is extruded out after deaerated; an air section is cooled down in a water bath to form an initial product; then the diluents are extracted to get the multi-pore product.
Description
Technical field
The present invention relates to a kind of preparation method of Kynoar doughnut perforated membrane.Porous membrane structure by this method preparation is even, and water flux and higher voidage can be used for aspects such as isolated by filtration, running water purification, waste water treating and reutilizing preferably.
Background technology
Membrane separation technique is to utilize film the infiltrative difference of each components selection in the mixture to be realized the new separation technology that separates, purifies and concentrate.Compare with traditional separation method, it is simple, easy and simple to handle that membrane separation technique has a device, energy savings, and the separative efficiency height, cost is low, characteristics such as remarkable in economical benefits.So film industry development in recent years is rapid, with the speed increase of annual 14%-15%.Particularly the development of high-performance diffusion barrier receives unprecedented concern especially.Because film in application process, need to adopt cleaning agent as: chemical substances such as clorox, strong acid and strong base are cleaned, so require membrane material to have excellent performance.
Kynoar (PVDF) has good heatproof, corrosion-resistant, resistance to oxidation, solvent resistance as a kind of novel fluoro-carbon thermoplastic.Can be applicable to adverse circumstances.Therefore, in recent years, people are developing and using with Kynoar is the diffusion barrier of main membrane material.
US Patent4,806,291 JP-A-7-265674 and CN1128176A have reported that a kind of usefulness does-method of wet method spinning Kynoar hollow-fibre membrane.Utilize this method to obtain a kind of high flux, larger aperture, be applicable to the Kynoar hollow-fibre membrane of medical and health, food industry.But be subjected to changing a social system the restriction of film method, film-strength is under some influence.Its application is restricted.
US Patent 6,299,773 and 5,022,990, and put down in writing among the CN1147352C Kynoar, organic matter liquid and a kind of inorganic matter melt blending, extruding spinning is shaped and obtains the hollow-fibre membrane of thick relatively diameter and relatively thick, this film has the tridimensional network of being made up of Kynoar fully, can be used for handling high viscosity liquid.But, this method complicated process of preparation, manufacturing cost is higher; And, cause the film defective easily owing to added inorganic particulate in the film-forming process.
CN1687222A discloses a kind of preparation method who prepares modified polyvinylidene fluoride separation membrane.It had both used the solvent of Kynoar on the basis of traditional wet method inversion of phases legal system film, form solution at a lower temperature, and added the hydrophilicity that hydrophilic inorganic particles is come modified polyvinilidene fluoride film in solution.Obtain a kind of more resistant to pollution polyvinylidene fluoride separation membrane.This method still can't overcome some shortcomings of conventional wet inversion of phases legal system film.Because the existence of inorganic particulate makes film occur defective hole easily.
CN1510180A and CN1621138A have reported that a kind of melt blending prepares the method for Kynoar hollow fiber microporous membrane.In this method film-forming process, do not adopt or adopt less organic solvent, utilizing stretches makes microphase-separated generation micropore prepare hollow-fibre membrane.But the gained membrane porosity is lower.Be not easy to be applied.
CN1481272A discloses the method that a kind of preparation has the hydrophilicity kynoar hollow-fibre membrane of chondritic.This method is that Kynoar and its poor solvent are formed solution at high temperature, cools off the formation perforated membrane that is separated.This method is in film-forming process, the exchange of material does not take place for solvent and cooling bath, is purely to induce being separated of generation and film forming by the exchange of heat.
CN1748844A has stated that thermal phase separation process prepares the method for polyvinylidene fluoride film.This method adopts single diluent to prepare perforated membrane, and the gained membrane flux is less, and inside is chondritic.Application is restricted.CA1792420A has used benzophenone and ester class diluent to prepare homogeneous spongelike structure polyvinylidene fluoride film, does not still mention performances such as membrane flux.
Sum up the preparation method of above Kynoar hollow-fibre membrane, mainly contain four kinds: (1) (doing) wet method phase inversion, this method be with polymer dissolution in its good solvent, form solution, extrude then, enter in a kind of non-solvent of polymer, this non-solvent can dissolve each other with solvent, so can cause the hollow-fibre membrane solidified forming with the exchange of solvent in the polymer solution.This is called non-solvent and induces and be separated.This method institute film forming is generally cortex construction, easily form macropore, mechanical strength lower (2) melt blending is in conjunction with the stripping extraction method, this method is with Kynoar, inorganic particulate and organic solvent melt blending, spinning, extract organic solvent and inorganic particulate with suitable chemical substance then, form three-dimensional porous structure, and can not form cortex construction, and manufacturing cost is higher.(3) stretching microphase-separated method, this method are utilized melt blending, microphase-separated, stretching pore-forming.The prepared membrane porosity of this method is lower, and water flux is less.(4) thermally induced phase separation, this method are that Kynoar and its diluent are formed solution at high temperature, and cooling, cooling make the solution formation perforated membrane that is separated.But for polyvinylidene fluoride material, because suitable single diluent is difficult to find, the membrane structure and the performance of preparation are unsatisfactory.
The inventor has furtherd investigate composite thinning agent to membrane structure and Effect on Performance according to phase separation principle, has obtained the polyvinylidene fluoride porous film of structure and better performances.
Summary of the invention
The objective of the invention is to overcome above-mentioned existing masking technique problem, propose a kind of method for preparing Kynoar doughnut perforated membrane.
The present invention relates to a kind of preparation method of polyvinylidene fluoride porous film, it is characterized in that: with melt index is that Kynoar raw material and the mixed diluent of 5-20 adds in the molten batch can, Kynoar content 20wt%-40wt%, the corresponding content 80wt%-60wt% of mixed diluent, mixed diluent is made up of cosolvent and organic non-solvent of Kynoar, wherein cosolvent is that high temperature can form homogeneous transparent solution and organic high boiling solvent of low temperature phase-splitting with Kynoar, non-solvent is not for dissolving the higher boiling organic liquid of Kynoar under any temperature, in the mixed solvent of Kynoar, the consumption of cosolvent is 20wt%-80wt%, non-solvent is 80wt%-20wt%, said mixture is dissolved 180 ℃ of-260 ℃ of high-temperature stirring, form clear solution, make casting solution after the deaeration, make flat sheet membrane or hollow-fibre membrane then.
Preparation in accordance with the present invention is characterized in that film-forming method is that casting solution is extruded by pressure, through measuring pump, doughnut spinning head, and the air section cooling, the water-bath cooling, reeling forms the initial goods of doughnut.Wherein 140 ℃-180 ℃ of air section temperature, length 0-100cm; Bath temperature 0-80 ℃.When the preparation flat sheet membrane, the environment knifing of fixed temperature must be arranged, 180 ℃-230 ℃ of environment temperatures, the knifing time of staying was controlled within 60 seconds, and the composite thinning agent in doughnut precursor or the flat sheet membrane is proposed by extraction, formed porous article.
Preparation in accordance with the present invention, the melt index that it is characterized in that polyvinylidene fluoride is 8.In the mixed solvent of Kynoar, the consumption of cosolvent is 40wt%-60wt%, and non-solvent is 60wt%-40wt%.
Preparation in accordance with the present invention, it is characterized in that cosolvent is repefral, dibutyl phthalate, diethylene glycol butyl ether, carbitol ester, propane diols carbonic ester, gamma-butyrolacton, 2,2,4-trimethyl-1, the mixture of one or more in the 3-pentanediol mono isobutyrate.
Preparation in accordance with the present invention is characterized in that used non-solvent is atoleine, dioctyl phthalate, diisooctyl phthalate, C
5～9Ethylene glycol fatty acid, C
7～9Aliphatic acid diethylene glycol (DEG) ester, soya-bean oil, peanut oil, C
8～20The mixture of one or more of long-chain fat alcohol ester.
Preparation in accordance with the present invention is characterized in that cosolvent is the mixture of repefral and dibutyl phthalate, perhaps the mixture of repefral and diethylene glycol butyl ether.
Preparation in accordance with the present invention is characterized in that non-solvent is dioctyl phthalate or diisooctyl phthalate.
By above method as can be seen, the present invention does not use or uses additive less, and filming technology is simple, and film forming condition is easy to control, made membrane structure homogeneous, excellent performance.Have higher water permeability, can be widely used in aspects such as isolated by filtration, running water purification, waste water treating and reutilizing.
Description of drawings
Fig. 1 is the cross-section structure of goods hollow-fibre membrane of the present invention.
Fig. 2 is the section amplification assumption diagram of goods hollow-fibre membrane of the present invention
Fig. 3 is the surface texture figure of goods hollow-fibre membrane of the present invention
The specific embodiment
In the cosolvent of Kynoar, add high temperature resistant organic non-solvent and form mixed diluent, regulate the intermiscibility of mixed diluent and Kynoar, promptly regulate the mode that is separated of composite thinning agent and Kynoar pyrosol, make it to take place liquid/liquid phase separation, be easy to obtain even loose structure.The cosolvent of indication of the present invention is that high temperature can form homogeneous transparent solution with Kynoar and low temperature can not form organic high boiling solvent of solution, and promptly high-temperature digestion forms solution, low temperature phase-splitting solidified forming; Used non-solvent is not for dissolving the higher boiling organic liquid of Kynoar under any temperature.
Kynoar is dissolved in the mixed diluent, and at least a in the mixed diluent is the cosolvent of Kynoar, and another kind is the non-solvent of Kynoar.The melt index of Kynoar (ASTM D1238) is 5-20, be preferably 8, in composition, Kynoar content 20wt%-40wt%, the corresponding content 80wt%-60wt% of mixed diluent, wherein cosolvent is 20%-80% in the mixed solvent of Kynoar, is preferably 40%-60%, and the non-solvent of Kynoar is 80%-20%, be preferably 60%-40%, under 180 ℃ of-260 ℃ of high temperature,, form clear solution, make casting solution after the deaeration the composition stirring and dissolving.
Here the cosolvent of indication is that high temperature can form homogeneous transparent solution and organic high boiling solvent of low temperature phase-splitting with Kynoar, be mainly repefral, dibutyl phthalate, diethylene glycol butyl ether, carbitol ester, propane diols carbonic ester, gamma-butyrolacton, 2,2,4-trimethyl-1, one or more in the 3-pentanediol mono isobutyrate; Used non-solvent comprises: atoleine, dioctyl phthalate, diisooctyl phthalate, C for can not dissolve the higher boiling organic liquid of Kynoar under any temperature
5～9Ethylene glycol fatty acid (0259 plasticizer), C
7～ 9Aliphatic acid diethylene glycol (DEG) ester (1279 plasticizer), soya-bean oil, peanut oil, C
8～20The mixture of one or more of long-chain fat alcohol ester.
Above-mentioned casting solution is extruded by pressure, through measuring pump, doughnut spinning head, the air section cooling, the water-bath cooling, reeling forms the initial goods of doughnut.Wherein 140 ℃-180 ℃ of air section temperature, length 0-100cm; Bath temperature 0-80 ℃.Perhaps with casting solution knifing in hot environment (being higher than 180 ℃), through 140 ℃ of-180 ℃ of air baths coolings, cool time 0.5-5min, 0 ℃ of-80 ℃ of water-baths cooling makes the initial flat panel film.Composite thinning agent in initial hollow-fibre membrane and the flat sheet membrane is proposed by extraction, form the porous hollow fiber membrane goods.
The preparation method of composite thinning agent of the present invention is: add high temperature resistant organic non-solvent and form composite thinning agent in the cosolvent of Kynoar, regulate the intermiscibility of composite thinning agent and Kynoar, promptly according to this system solution phasor, regulate the mode that is separated of composite thinning agent and Kynoar pyrosol, make it to take place liquid/liquid phase separation, be easy to obtain even loose structure.
The film surface and the inside of this invention preparation all have the uniform loose structure of form, and porosity is 60～85%, and the film water permeability is at 80～1000L.m under 0.1MPa pressure, 25 ℃ of conditions
-2.h
-1The internal diameter of hollow-fibre membrane is determined by rate of extrusion and coiling speed according to the different of application with the big I of external diameter.
The present invention characterizes to the polyvinylidene fluoride film microstructure with the water flux performance.Microstructure adopts SEM to carry out observational study; The water flux test condition is: precompressed with 25 ℃ of ultrafiltration water test water flux, was scaled the volume of elementary membrane area, unit interval institute's permeate water after 5 minutes under the 0.1MPa according to actual flow.
Embodiment 1: 25wt% Kynoar, 30wt% dibutyl phthalate, 15wt% diethyl phthalate, 30wt% dioctyl phthalate are put in the molten batch can jointly, be heated to 220 ℃, stirring and dissolving forms clear solution, discontinuous degassing 2 hours, knifing in 220 ℃ of environment is then directly put into 20 ℃ of water-bath cooling and shapings, is formed perforated membrane after extracting diluent.Film surface and internal structure are even, and water flux is 342L.m
-2.h
-1, porosity 82%.
Comparative Examples 1.1: the content of Kynoar among the embodiment 1 is increased to 30wt%, composite thinning agent form, constant rate, makes perforated membrane according to the film forming condition of embodiment 1.Membrane flux 215Lm
-2h
-1, voidage 77.5%.
Comparative Examples 1.2: Kynoar concentration among the embodiment 1 is increased to 35wt%, makes perforated membrane with quadrat method.Membrane flux 80L.m
-2h
-1, voidage 71%.
Comparative Examples 1.3: Kynoar concentration is risen to 40wt%, and solution viscosity is bigger, and knifing is difficulty comparatively.
Comparative Examples 1.4: according to the film forming condition of Comparative Examples 1.1, change the cooling bath temperature into 30 ℃, membrane flux is 260L.m
-2h
-1, voidage is 76.5%.
Comparative Examples 1.5: according to the film forming condition of Comparative Examples 1, change the cooling bath temperature into 50 ℃, membrane flux is 336L.m
-2h
-1, voidage is 75.4%.
Embodiment 2: 20wt% Kynoar, 30wt% dibutyl phthalate, 20wt% diethyl phthalate, 30wt% diisooctyl phthalate are placed molten batch can jointly, 200 ℃ of stirring and dissolving form clear solution, deaeration 2 hours, knifing in 200 ℃ of environment, directly immerse ice-water bath, form perforated membrane behind the extraction diluent.Membrane structure is even, water flux 1002L.m
-2h
-1, voidage 83%.
Embodiment 3: Kynoar, 30wt% dibutyl phthalate, 5wt% diethyl phthalate, the 33wt% diisooctyl phthalate of 32wt% are placed the molten batch can of spinning-drawing machine jointly, 220 ℃ of stirring and dissolving form clear solution, deaeration 4 hours, nitrogen is given and is pressed, extrude by measuring pump, spinning head, directly immerse 20 ℃ of water-baths, cooling, typing formation doughnut initial film, form the doughnut perforated membrane behind the extraction diluent.Membrane structure is even, water flux 206L.m
-2h
-1, voidage 76.3%.
Comparative Examples 3.1:, before as-spun fibre immerses cold bath, reserve 20cm air section length (23 ℃ of air themperatures), gained doughnut membrane flux 260L.m according to the film-forming method of embodiment 3
-2h
-1, voidage 74.3%
Comparative Examples 3.2: according to the film-forming method of embodiment 3, the doughnut of will coming into being immerses 60 ℃ of water-baths, and gained hollow-fibre membrane microstructure has the aggregation vestige, and is comparatively even.Water flux 221L.m
-2h
-1, voidage 75.2%.
Embodiment 4: 30wt% Kynoar, 40wt% repefral, 10wt% dibutyl ethylene glycol ether, 20wt% diisooctyl phthalate are placed molten batch can jointly, 220 ℃ of stirring and dissolving form clear solution, deaeration 2 hours, knifing in 220 ℃ of environment, directly immerse 20 ℃ of water-baths, form perforated membrane behind the extraction diluent.Membrane flux 176L.m
-2h
-1, voidage 73.5%.
Embodiment 5: 30wt% Kynoar, 30wt% dioctyl phthalate, 40wt% dibutyl ethylene glycol ether are placed molten batch can jointly, 190 ℃ of stirring and dissolving form clear solution, deaeration 2 hours, knifing in 200 ℃ of environment, directly immerse 20 ℃ of water-baths, form perforated membrane behind the extraction diluent.Membrane flux 96L.m
-2h
-1, voidage 70.5%.
Embodiment 6: Kynoar, 30wt% dibutyl phthalate, 5wt% dibutyl ethylene glycol ether, the 30wt% diisooctyl phthalate of 35wt% are placed the molten batch can of spinning-drawing machine jointly, 220 ℃ of stirring and dissolving form clear solution, deaeration 4 hours, nitrogen is given and is pressed, extrude by measuring pump, spinning head, directly immerse 20 ℃ of water-baths, cooling, typing formation doughnut initial film, form the doughnut perforated membrane behind the extraction diluent.Membrane structure is even, water flux 101L.m
-2h
-1, voidage 71.3%.
Claims (8)
1. the preparation method of a polyvinylidene fluoride porous film, it is characterized in that: with melt index is that Kynoar raw material and the mixed diluent of 5-20 adds in the molten batch can, Kynoar content 20wt%-40wt%, the corresponding content 80wt%-60wt% of mixed diluent, mixed diluent is made up of cosolvent and organic non-solvent of Kynoar, wherein cosolvent is that high temperature can form homogeneous transparent solution and organic high boiling solvent of low temperature phase-splitting with Kynoar, non-solvent is not for dissolving the higher boiling organic liquid of Kynoar under any temperature, in the mixed solvent of Kynoar, the consumption of cosolvent is 20wt%-80wt%, non-solvent is 80wt%-20wt%, said mixture is dissolved 180 ℃ of-260 ℃ of high-temperature stirring, form clear solution, make casting solution after the deaeration, make flat sheet membrane or hollow-fibre membrane then.
2. preparation method according to claim 1 is characterized in that film-forming method is that casting solution is extruded by pressure, through measuring pump, doughnut spinning head, and the air section cooling, the water-bath cooling, reeling forms the initial goods of doughnut.Wherein 140 ℃-180 ℃ of air section temperature, length 0-100cm; Bath temperature 0-80 ℃.When the preparation flat sheet membrane, the environment knifing of fixed temperature must be arranged, 180 ℃-230 ℃ of environment temperatures, the knifing time of staying was controlled within 60 seconds, and the composite thinning agent in doughnut precursor or the flat sheet membrane is proposed by extraction, formed porous article.
3. preparation method according to claim 1 and 2: the melt index that it is characterized in that polyvinylidene fluoride is 8.
4. preparation method according to claim 1 and 2: it is characterized in that in the mixed solvent of Kynoar the consumption of cosolvent is 40wt%-60wt%, non-solvent is 60wt%-40wt%.
5. according to the described preparation method of the arbitrary claim of claim 1～4: it is characterized in that cosolvent is repefral, dibutyl phthalate, diethylene glycol butyl ether, carbitol ester, propane diols carbonic ester, gamma-butyrolacton, 2,2,4-trimethyl-1, the mixture of one or more in the 3-pentanediol mono isobutyrate.
6. according to the described preparation method of the arbitrary claim of claim 1～3: it is characterized in that used non-solvent is atoleine, dioctyl phthalate, diisooctyl phthalate, C
5～9Ethylene glycol fatty acid, C
7～9Aliphatic acid diethylene glycol (DEG) ester, soya-bean oil, peanut oil, C
8～20The mixture of one or more of long-chain fat alcohol ester.
7. according to the described preparation method of the arbitrary claim of claim 1～3: it is characterized in that cosolvent is the mixture of repefral and dibutyl phthalate, perhaps the mixture of repefral and diethylene glycol butyl ether.
8. according to the described preparation method of the arbitrary claim of claim 1～3: it is characterized in that non-solvent is dioctyl phthalate or diisooctyl phthalate.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011116504A1 (en) * | 2010-03-26 | 2011-09-29 | 天津市塑料研究所 | Polyvinylidene fluoride hollow fiber separation membrane and manufacturing method thereof |
| CN105084463A (en) * | 2015-06-16 | 2015-11-25 | 厦门绿邦膜技术有限公司 | Hollow fiber oxygen dissolving film and assembly thereof |
| CN108939947A (en) * | 2018-08-06 | 2018-12-07 | 天津工业大学 | Kynoar and ultra-high molecular weight polyethylene blending microporous membrane and preparation method thereof |
| CN113198335A (en) * | 2021-04-21 | 2021-08-03 | 苏州富淼膜科技有限公司 | Polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof |
| CN113398780A (en) * | 2021-01-13 | 2021-09-17 | 杭州高通膜技术有限公司 | Preparation method of polyvinylidene fluoride hollow fiber membrane with ultrahigh tensile strength and anti-peeling strength and extrusion equipment thereof |
| CN113441018A (en) * | 2021-08-06 | 2021-09-28 | 苏州富淼膜科技有限公司 | Preparation method of polyvinylidene fluoride hollow fiber ultrafiltration membrane |
-
2006
- 2006-09-07 CN CNA2006101268376A patent/CN101138708A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011116504A1 (en) * | 2010-03-26 | 2011-09-29 | 天津市塑料研究所 | Polyvinylidene fluoride hollow fiber separation membrane and manufacturing method thereof |
| CN105084463A (en) * | 2015-06-16 | 2015-11-25 | 厦门绿邦膜技术有限公司 | Hollow fiber oxygen dissolving film and assembly thereof |
| CN105084463B (en) * | 2015-06-16 | 2017-08-04 | 厦门绿邦膜技术有限公司 | A kind of doughnut dissolved oxygen film and its component |
| CN108939947A (en) * | 2018-08-06 | 2018-12-07 | 天津工业大学 | Kynoar and ultra-high molecular weight polyethylene blending microporous membrane and preparation method thereof |
| CN108939947B (en) * | 2018-08-06 | 2020-12-04 | 天津工业大学 | Polyvinylidene fluoride and ultra-high molecular weight polyethylene blended microporous membrane and preparation method thereof |
| CN113398780A (en) * | 2021-01-13 | 2021-09-17 | 杭州高通膜技术有限公司 | Preparation method of polyvinylidene fluoride hollow fiber membrane with ultrahigh tensile strength and anti-peeling strength and extrusion equipment thereof |
| CN113198335A (en) * | 2021-04-21 | 2021-08-03 | 苏州富淼膜科技有限公司 | Polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof |
| CN113198335B (en) * | 2021-04-21 | 2023-08-04 | 苏州富淼膜科技有限公司 | Polyvinylidene fluoride hollow fiber ultrafiltration membrane and preparation method thereof |
| CN113441018A (en) * | 2021-08-06 | 2021-09-28 | 苏州富淼膜科技有限公司 | Preparation method of polyvinylidene fluoride hollow fiber ultrafiltration membrane |
| CN113441018B (en) * | 2021-08-06 | 2023-08-04 | 苏州富淼膜科技有限公司 | Preparation method of polyvinylidene fluoride hollow fiber ultrafiltration membrane |
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Application publication date: 20080312 |