CN109289545A - A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane - Google Patents
A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane Download PDFInfo
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- CN109289545A CN109289545A CN201811218064.3A CN201811218064A CN109289545A CN 109289545 A CN109289545 A CN 109289545A CN 201811218064 A CN201811218064 A CN 201811218064A CN 109289545 A CN109289545 A CN 109289545A
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- hollow fiber
- diluent
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- polyvinylidene fluoride
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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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/147—Microfiltration
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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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane, include the following steps preparation: (1) by Kynoar, polyethylene glycol, diluent, nanometer silicon carbide mixing, it is heated to 150-170 DEG C, it is uniformly mixed, casting solution is made, wherein Kynoar concentration is 20wt.%~35wt.%, Polyethylene glycol is 5wt.%~10wt.%, diluent concentration is 40wt.%~70wt.%, nano silicon carbide silicon concentration is 5wt.%~20wt.%, the diluent is benzyl alcohol, gaultherolin, cyclohexanone, cyclohexanol, at least one of diethyl malonate；(2) casting solution that step (1) obtains is injected into tube-type hollow fiber spinning spray head silk with metering pump, the doughnut squeezed out through spray head silk immerses 20 DEG C~60 DEG C of cooling bath, it exchanges diluent with cooling bath and cooling and extraction process occurs simultaneously, be solidified into polyvinylidene fluoride hollow fiber microporous membrane.The method of the present invention is easy to operate, and polyvinylidene fluoride hollow fiber microporous membrane obtained has high-purity water flux and compressive property.
Description
Technical field
The present invention relates to field of compound material, and in particular to a kind of preparation side of polyvinylidene fluoride hollow fiber microporous membrane
Method.
Background technique
Hollow Fiber Membrane Separation Technology is a kind of new and high technology to grow up in mid-twentieth century, nearly two, 30 years
Come, has obtained development at full speed in the world, membrane separation technique is being that the mankind bring huge interests, and hollow-fibre membrane is because of it
The characteristics of height filling density and separative efficiency, is concerned.It is compared to the film of the other forms such as plate membrane, rolled film, hollow fibre
Dimension film have the advantages that unit volume loading density greatly and self-supporting.Nowadays, the external pressing type hollow fibrous membrane of China's domestic production
Component and complete separator, have had reached the advanced level of same kind of products at abroad.
Kynoar (PVDF) is the high molecular material of function admirable, due to its excellent mechanical strength and chemical stabilization
Property, in special isolating environment, polytetrafluoroethylene (PTFE) is a kind of ideal separating and filtering material, in recent years in membrane separation technique
Gradually paid attention to by people.Hypochlorous corrosion in municipal wastewater is resistant to for it, therefore PVDF microporous barrier is widely used in pure water
Manufacture and sewage treatment.PVDF has solubility in organic solvent and the viscosity in fusion point also more low excellent simultaneously
Point, it is soluble in acetone, in dimethyl acetamide (DMAC) equal solvent, therefore can be formed a film using wet spinning.
Producing PVDF microporous barrier mainly has following report at present:
One, composite thinning agent not soluble in water is extracted using alcohol or ether extractant, needs to wash using water after extraction
Remaining alcohol or ether extractant in film, the extraction process it is complex and film the cost is relatively high；
Two, increase the hydrophily of film, but phase by the hydrophily of blending improvement pvdf membrane and the method for antifouling property
Than in this method of the present invention, there are insufficient features complicated for operation；
Three, using the mixed of the alcohols non-solvent of the high-temperature solvent diphenyl carbonate of Kynoar and Kynoar composition
Bonding solvent is diluent, and the uniform spongelike structure polyvinylidene fluoride film with high intensity, high porosity, high throughput is made, but
The higher ultrafiltration membrane of separation accuracy can not be made in polyvinylidene fluoride film made from this method；
Four, hollow-fibre membrane Enhancement Method has through the external film in woven tube, forms the composite membrane with supporting layer,
But method is not easy enough.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of preparations of polyvinylidene fluoride hollow fiber microporous membrane
Method, this method is easy to operate, and polyvinylidene fluoride hollow fiber microporous membrane obtained has high-purity water flux and compressive property.
Technical solution of the present invention is as following manner is realized:
A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane, includes the following steps preparation:
(1) Kynoar, polyethylene glycol, diluent, nanometer silicon carbide are mixed, is heated to 150-170 DEG C, stirs
It mixes uniformly mixed, casting solution is made, wherein Kynoar concentration is 20wt.%~35wt.%, and Polyethylene glycol is
5wt.%~10wt.%, diluent concentration are 40wt.%~70wt.%, and nano silicon carbide silicon concentration is 5wt.%~20wt.%,
The diluent is at least one of benzyl alcohol, gaultherolin, cyclohexanone, cyclohexanol, diethyl malonate；
(2) casting solution that step (1) obtains is injected into tube-type hollow fiber spinning spray head silk with metering pump, through spray head
The doughnut that silk squeezes out immerses 20 DEG C~60 DEG C of cooling bath, make diluent exchanged with cooling bath occur to cool down simultaneously and
Extraction process is solidified into polyvinylidene fluoride hollow fiber microporous membrane.
In step (1) of the present invention, in the casting solution, each component proportion especially wherein the content of polyethylene glycol for
The mean pore size of polyvinylidene fluoride hollow fiber microporous membrane has great influence, finally influences polyvinylidene fluoride hollow fiber
The compressive property and pure water flux of microporous barrier.The preferred Kynoar concentration of the present invention is 20wt.%~35wt.%, poly- second two
Determining alcohol be 6wt.%~7wt.%, diluent concentration be 50wt.%~69wt.%, nano silicon carbide silicon concentration be 5wt.%~
10wt.%；Most preferably Kynoar concentration is 22.5wt.%, Polyethylene glycol 6.5wt.%, and diluent is
66wt.%, nano silicon carbide silicon concentration are 5wt.%.
In step (1) of the present invention, the diluent is preferably benzyl alcohol, gaultherolin, cyclohexanone, cyclohexanol, third
Any two kinds of combination in diethyl adipate.
In step (2) of the present invention, the temperature by controlling cooling bath can control polyvinylidene fluoride hollow fiber micropore
The pore size of film, the final compressive property and pure water flux for influencing polyvinylidene fluoride hollow fiber microporous membrane.The present invention is preferred
The temperature of cooling bath is 20 DEG C.
In step (3) of the present invention, the surface average pore size of the polyvinylidene fluoride hollow fiber microporous membrane is
10nm~0.2 μm, porosity are 50%~70%.
Compared with the prior art, the present invention has the advantages that
(1) present invention uses water-soluble diluent, and using water as cooling bath and spe medium, is greatly simplified
Processing step shortens technique film time.
(2) nanometer silicon carbide is added in formula of casting is inorganic additive, greatly improves the crushing resistance of film wire
Energy.
Detailed description of the invention
The film section structure of polyvinylidene fluoride hollow fiber microporous membrane made from 1 embodiment 1 of attached drawing.
The film section part enlarged structure of polyvinylidene fluoride hollow fiber microporous membrane made from 2 embodiment 1 of attached drawing.
The film section enlarged structure of polyvinylidene fluoride hollow fiber microporous membrane made from 3 embodiment 1 of attached drawing.
Specific embodiment
Technical solution of the present invention is further detailed below with reference to specific example, but protection scope of the present invention
It is without being limited thereto:
The raw material sources that the embodiment of the present invention uses are as shown in the table:
| Reagent name | The place of production |
| Kynoar | Dongguan City Jing Tian plastic material Co., Ltd, Guangdong |
| Polyethylene glycol (molecular weight 1000) | Shanghai Ling Feng chemical reagent Co., Ltd, Shanghai |
| Benzyl alcohol | Aladdin reagent, Shanghai |
| Gaultherolin | Aladdin reagent, Shanghai |
| Cyclohexanone | Aladdin reagent, Shanghai |
| Cyclohexanol | Aladdin reagent, Shanghai |
| Diethyl malonate | Aladdin reagent, Shanghai |
| Nanometer silicon carbide | Aladdin reagent, Shanghai |
Embodiment 1
By Kynoar (weight average molecular weight 800000) and gaultherolin and benzyl alcohol, proportion is polyvinylidene fluoride
Alkene mass percent is 35wt.%, and gaultherolin mass percent is 30wt.%, and the mass percent of benzyl alcohol is
24wt.%, the mass percent 6wt.% of polyethylene glycol, nano silicon carbide silicon concentration are 5wt.%, are put into high-temperature stirring kettle and add
Heat is warming up to 150 DEG C, is uniformly mixed.Hollow fibre is made by tube-type hollow fiber spinning spray head silk in mixture solution again
Shape is tieed up, and enters in 20 DEG C of cooling bath and makes solution split-phase film-forming, is completed at the same time extraction process in cooling procedure,
Polyvinylidene fluoride hollow fiber microporous membrane is made.
It is tested and is measured it is found that the film section of polyvinylidene fluoride hollow fiber microporous membrane obtained is in spongelike structure, hole
Gap rate is 52.3%, breaking strength 12.9MPa, and surface average pore size is 0.2 μm, and 25 DEG C of pure water flux is at 0.1MPa
1490L/m2h。
Embodiment 2
By Kynoar (weight average molecular weight 1000000) and gaultherolin and benzyl alcohol, proportion is to gather inclined fluorine
Ethylene mass percentage is 22.5wt.%, and gaultherolin mass percent is 31wt.%, and the mass percent of benzyl alcohol is
35wt.%, the mass percent 6.5wt.% of polyethylene glycol, nano silicon carbide silicon concentration are 5wt.%, are put into high-temperature stirring kettle
150 DEG C are heated to, is uniformly mixed.Mixture solution is made up of tube-type hollow fiber spinning spray head silk again hollow
Threadiness, and enter in 20 DEG C of cooling bath and make solution split-phase film-forming, it is completed at the same time extracted in cooling procedure
Polyvinylidene fluoride hollow fiber microporous membrane is made in journey.
It is tested and is measured it is found that the film section of polyvinylidene fluoride hollow fiber microporous membrane obtained is in spongelike structure, hole
Gap rate is 51.3%, breaking strength 13.9MPa, and surface average pore size is 0.2 μm, and 25 DEG C of pure water flux is at 0.1MPa
1590L/m2h。
Embodiment 3
By Kynoar (weight average molecular weight 500000) and gaultherolin and benzyl alcohol, proportion is polyvinylidene fluoride
Alkene mass percent is 25wt.%, and gaultherolin mass percent is 30wt.%, and the mass percent of benzyl alcohol is
30wt.%, the mass percent 10wt.% of polyethylene glycol, nano silicon carbide silicon concentration are 5wt.%, are put into high-temperature stirring kettle and add
Heat is warming up to 170 DEG C, is uniformly mixed.Hollow fibre is made by tube-type hollow fiber spinning spray head silk in mixture solution again
Shape is tieed up, and enters in 50 DEG C of cooling bath and makes solution split-phase film-forming, is completed at the same time extraction process in cooling procedure,
Polyvinylidene fluoride hollow fiber microporous membrane is made.
It is tested and is measured it is found that the film section of polyvinylidene fluoride hollow fiber microporous membrane obtained is in spongelike structure, hole
Gap rate is 60.2%, and breaking strength 9.9MPa, surface average pore size is 21nm, and 25 DEG C of pure water flux is at 0.1MPa
425L/m2h。
Embodiment 4
By Kynoar (weight average molecular weight 1000000) and gaultherolin and benzyl alcohol, proportion is to gather inclined fluorine
Ethylene mass percentage is 22.5wt.%, and cyclohexanone mass percent is 31wt.%, and the mass percent of cyclohexanol is
35wt.%, the mass percent 6.5wt.% of polyethylene glycol, nano silicon carbide silicon concentration are 5wt.%, are put into high-temperature stirring kettle
170 DEG C are heated to, is uniformly mixed.Mixture solution is made up of tube-type hollow fiber spinning spray head silk again hollow
Threadiness, and enter in 20 DEG C of cooling bath and make solution split-phase film-forming, it is completed at the same time extracted in cooling procedure
Polyvinylidene fluoride hollow fiber microporous membrane is made in journey.
It is tested and is measured it is found that the film section of polyvinylidene fluoride hollow fiber microporous membrane obtained is in spongelike structure, hole
Gap rate is 60.2%, and breaking strength 14.1MPa, surface average pore size is 0.2nm, and 25 DEG C of pure water flux is at 0.1MPa
1533L/m2h。
Embodiment 5
By Kynoar (weight average molecular weight 700000) and gaultherolin and benzyl alcohol, proportion is polyvinylidene fluoride
Alkene mass percent is 25wt.%, and cyclohexanone mass percent is 30wt.%, and the mass percent of benzyl alcohol is 30wt.%,
The mass percent 10wt.% of polyethylene glycol, nano silicon carbide silicon concentration are 5wt.%, are put into high-temperature stirring kettle and are heated to
It 170 DEG C, is uniformly mixed.Hollow fiber is made by tube-type hollow fiber spinning spray head silk in mixture solution again, and
Entering in 50 DEG C of cooling bath makes solution split-phase film-forming, is completed at the same time extraction process in cooling procedure, is made poly-
Vinylidene hollow fiber microporous membrane.
It is tested and is measured it is found that the film section of polyvinylidene fluoride hollow fiber microporous membrane obtained is in spongelike structure, hole
Gap rate is 62.1%, and breaking strength 12.1MPa, surface average pore size is 12nm, and 25 DEG C of pure water flux is at 0.1MPa
412L/m2h。
The above experimental result of Comprehensive Correlation can obtain, and the best film formula of the experiment is that Kynoar mass percent is
22.5wt.%, gaultherolin mass percent are 31wt.%, and the mass percent of benzyl alcohol is 35wt.%, polyethylene glycol
Mass percent 6.5wt.%, nano silicon carbide silicon concentration be 5wt.%.Film properties obtained are best under this condition, have good
Film-strength and higher water flux.
Obviously, embodiment described above is just to clearly express the case that the present invention is lifted, not to of the invention
Embodiment sets qualifications.Equivalent changes and modifications made by all contents according to the application the scope of the patents are in this hair
Within bright protection scope.
Claims (5)
1. a kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane, includes the following steps preparation:
(1) Kynoar, polyethylene glycol, diluent, nanometer silicon carbide are mixed, is heated to 150-170 DEG C, stirring is mixed
Close uniformly, be made casting solution, wherein Kynoar concentration be 20wt.%~35wt.%, Polyethylene glycol be 5wt.%~
10wt.%, diluent concentration are 40wt.%~70wt.%, and nano silicon carbide silicon concentration is 5wt.%~20wt.%, and described is dilute
Releasing agent is at least one of benzyl alcohol, gaultherolin, cyclohexanone, cyclohexanol, diethyl malonate；
(2) casting solution that step (1) obtains is injected into tube-type hollow fiber spinning spray head silk with metering pump, is squeezed through spray head silk
Doughnut out immerses 20 DEG C~60 DEG C of cooling bath, exchanges diluent with cooling bath and occurs cooling simultaneously and extract
Process is solidified into polyvinylidene fluoride hollow fiber microporous membrane.
2. preparation method as described in claim 1, it is characterised in that: in step (1), in the casting solution, Kynoar
Concentration be 20wt.%~35wt.%, Polyethylene glycol be 6wt.%~7wt.%, diluent concentration be 50wt.%~
69wt.%, nano silicon carbide silicon concentration are 5wt.%~10wt.%.
3. preparation method as described in claim 1, it is characterised in that: in step (1), in the casting solution, Kynoar
Concentration is 22.5wt.%, Polyethylene glycol 6.5wt.%, diluent 66wt.%, and nano silicon carbide silicon concentration is
5wt.%.
4. the preparation method as described in one of claims 1 to 3, it is characterised in that: in step (1), the diluent is benzene
Methanol, gaultherolin, cyclohexanone, cyclohexanol, any two kinds of combination in diethyl malonate.
5. the preparation method as described in one of claims 1 to 3, it is characterised in that: in step (2), the temperature of cooling bath is
20℃。
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| CN201811218064.3A CN109289545A (en) | 2018-10-18 | 2018-10-18 | A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane |
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| CN201811218064.3A CN109289545A (en) | 2018-10-18 | 2018-10-18 | A kind of preparation method of polyvinylidene fluoride hollow fiber microporous membrane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114733363A (en) * | 2021-01-07 | 2022-07-12 | 杭州费尔新材料有限公司 | Preparation process of polyolefin gas exchange membrane |
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|---|---|---|---|---|
| CN102019148A (en) * | 2010-12-23 | 2011-04-20 | 东华大学 | Preparation method of polyvinylidene fluoride blended membrane |
| CN102836645A (en) * | 2012-09-18 | 2012-12-26 | 中国华电工程(集团)有限公司 | Polyvinylidene-fluoride hollow fibre membrane and preparation method thereof |
| CN104043344A (en) * | 2013-03-15 | 2014-09-17 | 中化蓝天集团有限公司 | Polyvinylidene fluoride hollow fiber microporous membrane and preparation method |
| KR101536585B1 (en) * | 2013-09-30 | 2015-07-22 | (주)티피에스 | Method for manufacturing hollw fiber membrane and hollow fiber membrane using same |
| CN107096395A (en) * | 2017-05-19 | 2017-08-29 | 开源环保（集团）有限公司 | A kind of reinforced type polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof |
-
2018
- 2018-10-18 CN CN201811218064.3A patent/CN109289545A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102019148A (en) * | 2010-12-23 | 2011-04-20 | 东华大学 | Preparation method of polyvinylidene fluoride blended membrane |
| CN102836645A (en) * | 2012-09-18 | 2012-12-26 | 中国华电工程(集团)有限公司 | Polyvinylidene-fluoride hollow fibre membrane and preparation method thereof |
| CN104043344A (en) * | 2013-03-15 | 2014-09-17 | 中化蓝天集团有限公司 | Polyvinylidene fluoride hollow fiber microporous membrane and preparation method |
| KR101536585B1 (en) * | 2013-09-30 | 2015-07-22 | (주)티피에스 | Method for manufacturing hollw fiber membrane and hollow fiber membrane using same |
| CN107096395A (en) * | 2017-05-19 | 2017-08-29 | 开源环保（集团）有限公司 | A kind of reinforced type polyvinylidene fluoride hollow fiber miillpore filter and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114733363A (en) * | 2021-01-07 | 2022-07-12 | 杭州费尔新材料有限公司 | Preparation process of polyolefin gas exchange membrane |
| CN114733363B (en) * | 2021-01-07 | 2023-10-31 | 杭州费尔新材料有限公司 | Preparation process of polyolefin gas exchange membrane |
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