CN109806777A - A kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film - Google Patents
A kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film Download PDFInfo
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- CN109806777A CN109806777A CN201711175301.8A CN201711175301A CN109806777A CN 109806777 A CN109806777 A CN 109806777A CN 201711175301 A CN201711175301 A CN 201711175301A CN 109806777 A CN109806777 A CN 109806777A
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Abstract
The invention discloses a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film, includes the following steps: to prepare casting solution, prepare hollow braided rope, prepare reinforcement, preparing primary hollow tunica fibrosa, preparation reinforcement basement membrane and prepare hollow-fibre membrane；The present invention has many advantages, such as that process is simple, high-efficient, the film of preparation has excellent corrosion-resistant, heat-resisting, cold-resistant, resistance to oxidation, weather resistance simultaneously, there to be selection block contaminants, and prevent or reduce pollutant in the irreversible deposition of film surface, improve the antifouling property of film；Solving the problems, such as hollow-fibre membrane, cortex is caducous in use, using the polyacrylonitrile filament with polyvinylidene fluoride surface separating layer with cosolvent characteristic, it is woven into reinforcement of the hollow tubular fabric as film, casting solution has preferable wellability to reinforcement, reinforcement fiber gap is penetrated into part, a possibility that increasing mechanical bonding strength, can reducing fracture of wire and stifled dirt, extends the service life of diaphragm.
Description
Technical field
The present invention relates to hollow-fibre membrane manufacturing technology field, specially a kind of reinforced type polyvinylidene fluoride hollow fiber film
Preparation method.
Background technique
With the rapid growth of social economy, the worsening shortages of water resource, which have become, restricts the important of economy and society development
Factor.UF membrane purification techniques because its with separative efficiency high, equipment be simple and convenient to operate, high degree of automation, without secondary dirt
The advantages that dye, therefore there are great advantage and potentiality in environment protection fields such as water process.Macromolecule organic film is carried on a shoulder pole in UF membrane field
As key player, and its manufacture craft is simple, membrane material kind is more diversified.Pvdf Microporous Hollow Fiber Membrane is utilized and is related to
And range it is wide, can be applied to the numerous areas such as medicine, health, electronics, food, sewage treatment, sea water desalination, especially
Purposes in sewage treatment, Treated sewage reusing and sea water desalination is even more to attract attention.But it was actually using
Cheng Zhong, membrane separation process handle the higher cost of water.The method for reducing cost generallyd use in the prior art usually passes through drop
The manufacturing cost of low membrane module, but increase the production water of per membrane area, realize that the operation under low pressure conditions is also to reduce
One of method of cost.Therefore, the Pvdf Microporous Hollow Fiber Membrane for manufacturing a kind of high throughput becomes research emphasis；Doughnut
Film has many advantages such as loading density height, self-supporting and is widely used in Industrial Wastewater Treatment, sewage reuse, sea
All various aspects such as water desalination pretreatment.In use, Yao Fanfu is subjected to the shock vibration of great deal running water, air-flow, easily
Fracture distress occurs, influences treatment effect, also brings detrimental effect to subsequent unit operation.Existing ultrafiltration membrane, seperation film, in
The corrosion-resistant, heat-resisting, cold-resistant of empty fiber membrane, resistance to oxidation, weather resistance are all to be improved.
So how to design a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film, becomes us and currently want
It solves the problems, such as.
Summary of the invention
The present invention provides a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film, the simple, efficiency with process
The advantages that high, while the film prepared has excellent corrosion-resistant, heat-resisting, cold-resistant, resistance to oxidation, weather resistance, will have selection to obstruct
Pollutant prevents or reduces pollutant in the irreversible deposition of film surface, improves the antifouling property of film；Solves hollow fibre
The film caducous problem of cortex in use is tieed up, there is the poly- of cosolvent characteristic using with polyvinylidene fluoride surface separating layer
Acrylic filament, is woven into reinforcement of the hollow tubular fabric as film, and casting solution has preferable wellability, part to reinforcement
A possibility that penetrating into reinforcement fiber gap, increase mechanical bonding strength, can reducing fracture of wire and stifled dirt, extend diaphragm uses the longevity
Life, can effectively solve the problems in above-mentioned background technique.
To achieve the above object, the invention provides the following technical scheme: a kind of reinforced type polyvinylidene fluoride hollow fiber film
Preparation method, include the following steps:
1) casting solution is prepared: after Kynoar, inorganic additive, pore-foaming agent, coupling agent, initiator and solvent are mixed
Ultrasonic wave disperses 30-60min at 60-80 DEG C, obtains solution；Organic additive is added in solution, stirring and dissolving, specifically
To stir 8h in the 60-80 DEG C of mixing speed with 200-400r/min, 80-90 DEG C of stirring 2-5h is then heated to, then cool to
70-80 DEG C stirring 6-10 hours, through filtering and deaeration after obtain casting solution；
2) it prepares hollow braided rope: being the immersion of 10% sodium hydrate aqueous solution with mass concentration under conditions of 30-80 DEG C
Hollow braided rope 0.5h-1h is handled to remove the greasy dirt on surface, washing is taken out and dries for use；With atmospheric pressure plasma jet treatment through locating
The hollow braided rope managed；
3) it prepares reinforcement: being required according to properties of product, yarn needed for selecting measures negative cruvature in reinforcement cross section
The side length on side, by the method for equivalent length of side by negative cruvature when being equivalent to positive camber and with the cross-sectional shape design group after equivalent
Core model is closed, weaves reinforcement on braider by core model of above-mentioned combination die, the equivalent core model in composite core formwork is taken out and makes to increase
Strong show consideration for is attached on the core model not taken out, and then taking out remaining core model can be obtained required reinforcement, i.e., by polyacrylonitrile fibre
Dimension is woven into hollow woven tube, the reinforcement as reinforced type polyvinylidene fluoride hollow fiber film；
4) it prepares primary hollow tunica fibrosa: casting solution obtained above being passed through to dry and wet spinning equipment together with core liquid and is carried out
Spinning is arranged on moving track wherein the electrospinning device includes: multiple moving tracks and multiple spinning-nozzles to move
It is moved on the length direction in dynamic rail road；The electrospinning device further includes being integrated to the end of moving track in its longitudinal direction
The trapped orbit in portion, wherein moving track moves in the width direction along trapped orbit；Wherein, trapped orbit has shape
At in holding tank wherein, voltage transmission bar is inserted and secured in holding tank；Wherein, moving track is in its longitudinal direction
End contact voltage transmission pole and be integrated to trapped orbit, to cover voltage transmission bar, be prepared into primary hollow tunica fibrosa；
5) it prepares reinforcement basement membrane: being used primary hollow tunica fibrosa is prepared in the reinforcement and step 4) that prepare in step 3)
Water impregnates, and is dried after being protected hole agent processing, obtains reinforcement basement membrane；
6) hollow-fibre membrane is prepared: it is dry after reinforcement basement membrane is cleaned with neutral detergent, then with low pole organic liquor
Body infiltrates it, and solvent and water 0-30: 70-100 are then prepared coagulation bath by mass percentage；In processed
Empty kernmantle and the casting solution of preparation pass through spinning head extrusion simultaneously, coagulation forming or are coagulated after first passing through the dry-spinning path of 1-15cm again
Gu molding, then receive silk；Reinforcement basement membrane obtained is impregnated into 12-24h in 10 DEG C -40 DEG C of deionized water, to remove casting film
Solvent and part pore former in liquid system dry up to reinforced type polyvinylidene fluoride hollow fiber film.
According to the above technical scheme, the Kynoar, inorganic additive, organic additive agent, pore-foaming agent, coupling
Agent, initiator, solvent and protect hole agent mass parts be Kynoar 40-50 parts, 10-15 parts of inorganic additive, organic addition
10-15 parts of hole agent of 10-15 parts of agent, 10-15 parts of pore-foaming agent, 5-10 parts of coupling agent, 5-10 parts of initiator, 10-15 parts of solvent and guarantor.
According to the above technical scheme, the inorganic additive is lithium chloride, sodium chloride, titanium chloride, titanium dioxide, titanium dioxide
One of silicon and graphene oxide or a variety of combinations.
According to the above technical scheme, the organic additive is polyvinylpyrrolidone, polyethylene glycol, sulfonated polysulfone, gathers
One of vinyl alcohol, polyacrylonitrile and polymethyl methacrylate or a variety of combinations.
According to the above technical scheme, the atmospheric pressure plasma jet treatment condition of the step 2) are as follows: jet diameters 2.5cm,
Sprinkler height is 2mm, and discharge gas can be air, nitrogen, argon gas, oxygen, the mixture of one or both of helium, gas
Body flow is 1-20L/min, supply frequency 5-20KHz, voltage 3-20kV, processing speed 2-10m/min.
According to the above technical scheme, moving track is located in parallel to one another in the step 4), wherein in moving track
It is each provided with the shifting chute for penetrating its center, and spinning-nozzle is inserted into and is arranged in shifting chute, wherein shifting chute exists
It is continuously formed on the length direction of moving track；The electrospinning device further includes pseudo- nozzle, and the puppet nozzle setting is moving
On dynamic rail road, with the outside for the outermost spinning-nozzle being arranged in the multiple spinning-nozzle.
According to the above technical scheme, the extrusion temperature in the step 6) is 20-80 DEG C；The spinning head specification: inner hole
For 1.3-3.4mm, exit orifice 1.4-3.6mm；The dry-spinning path temperature is 10-40 DEG C, relative humidity 30-99%RH；It is described
Setting temperature is 20-80 DEG C；The receipts silk speed is 2-10m/min.
Compared with prior art, beneficial effects of the present invention: having many advantages, such as that process is simple, high-efficient, while preparing
Film has excellent corrosion-resistant, heat-resisting, cold-resistant, resistance to oxidation, weather resistance, will have selection block contaminants, prevents or reduces dirt
Object is contaminated in the irreversible deposition of film surface, improves the antifouling property of film；Solves hollow-fibre membrane skin in use
The caducous problem of layer is woven into using the polyacrylonitrile filament with polyvinylidene fluoride surface separating layer with cosolvent characteristic
Reinforcement of the hollow tubular fabric as film, casting solution have preferable wellability to reinforcement, and part is penetrated between reinforcement fiber
A possibility that gap increases mechanical bonding strength, can reduce fracture of wire and stifled dirt, extends the service life of diaphragm.
Detailed description of the invention
Attached drawing is used to provide further understanding of the present invention, and constitutes part of specification, with reality of the invention
It applies example to be used to explain the present invention together, not be construed as limiting the invention.
In the accompanying drawings:
Fig. 1 is preparation flow figure of the invention.
Specific embodiment
Hereinafter, preferred embodiments of the present invention will be described with reference to the accompanying drawings, it should be understood that preferred reality described herein
Apply example only for the purpose of illustrating and explaining the present invention and is not intended to limit the present invention.
Embodiment: as shown in Figure 1, the present invention provides a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film,
Include the following steps:
1) casting solution is prepared: after Kynoar, inorganic additive, pore-foaming agent, coupling agent, initiator and solvent are mixed
Ultrasonic wave disperses 30-60min at 60-80 DEG C, obtains solution；Organic additive is added in solution, stirring and dissolving, specifically
To stir 8h in the 60-80 DEG C of mixing speed with 200-400r/min, 80-90 DEG C of stirring 2-5h is then heated to, then cool to
70-80 DEG C stirring 6-10 hours, through filtering and deaeration after obtain casting solution；
2) it prepares hollow braided rope: being the immersion of 10% sodium hydrate aqueous solution with mass concentration under conditions of 30-80 DEG C
Hollow braided rope 0.5h-1h is handled to remove the greasy dirt on surface, washing is taken out and dries for use；With atmospheric pressure plasma jet treatment through locating
The hollow braided rope managed；
3) it prepares reinforcement: being required according to properties of product, yarn needed for selecting measures negative cruvature in reinforcement cross section
The side length on side, by the method for equivalent length of side by negative cruvature when being equivalent to positive camber and with the cross-sectional shape design group after equivalent
Core model is closed, weaves reinforcement on braider by core model of above-mentioned combination die, the equivalent core model in composite core formwork is taken out and makes to increase
Strong show consideration for is attached on the core model not taken out, and then taking out remaining core model can be obtained required reinforcement, i.e., by polyacrylonitrile fibre
Dimension is woven into hollow woven tube, the reinforcement as reinforced type polyvinylidene fluoride hollow fiber film；
4) it prepares primary hollow tunica fibrosa: casting solution obtained above being passed through to dry and wet spinning equipment together with core liquid and is carried out
Spinning is arranged on moving track wherein the electrospinning device includes: multiple moving tracks and multiple spinning-nozzles to move
It is moved on the length direction in dynamic rail road；The electrospinning device further includes being integrated to the end of moving track in its longitudinal direction
The trapped orbit in portion, wherein moving track moves in the width direction along trapped orbit；Wherein, trapped orbit has shape
At in holding tank wherein, voltage transmission bar is inserted and secured in holding tank；Wherein, moving track is in its longitudinal direction
End contact voltage transmission pole and be integrated to trapped orbit, to cover voltage transmission bar, be prepared into primary hollow tunica fibrosa；
5) it prepares reinforcement basement membrane: being used primary hollow tunica fibrosa is prepared in the reinforcement and step 4) that prepare in step 3)
Water impregnates, and is dried after being protected hole agent processing, obtains reinforcement basement membrane；
6) hollow-fibre membrane is prepared: it is dry after reinforcement basement membrane is cleaned with neutral detergent, then with low pole organic liquor
Body infiltrates it, and solvent and water 0-30: 70-100 are then prepared coagulation bath by mass percentage；In processed
Empty kernmantle and the casting solution of preparation pass through spinning head extrusion simultaneously, coagulation forming or are coagulated after first passing through the dry-spinning path of 1-15cm again
Gu molding, then receive silk；Reinforcement basement membrane obtained is impregnated into 12-24h in 10 DEG C -40 DEG C of deionized water, to remove casting film
Solvent and part pore former in liquid system dry up to reinforced type polyvinylidene fluoride hollow fiber film.
According to the above technical scheme, the Kynoar, inorganic additive, organic additive agent, pore-foaming agent, coupling
Agent, initiator, solvent and protect hole agent mass parts be 40 parts of Kynoar, 10 parts of inorganic additive, 10 parts of organic additive,
10 parts of hole agent of 10 parts of pore-foaming agent, 5 parts of coupling agent, 5 parts of initiator, 10 parts of solvent and guarantor.
According to the above technical scheme, the inorganic additive is lithium chloride, sodium chloride, titanium chloride, titanium dioxide, titanium dioxide
One of silicon and graphene oxide or a variety of combinations.
According to the above technical scheme, the organic additive is polyvinylpyrrolidone, polyethylene glycol, sulfonated polysulfone, gathers
One of vinyl alcohol, polyacrylonitrile and polymethyl methacrylate or a variety of combinations.
According to the above technical scheme, the atmospheric pressure plasma jet treatment condition of the step 2) are as follows: jet diameters 2.5cm,
Sprinkler height is 2mm, and discharge gas can be air, nitrogen, argon gas, oxygen, the mixture of one or both of helium, gas
Body flow is 1-20L/min, supply frequency 5-20KHz, voltage 3-20kV, processing speed 2-10m/min.
According to the above technical scheme, moving track is located in parallel to one another in the step 4), wherein in moving track
It is each provided with the shifting chute for penetrating its center, and spinning-nozzle is inserted into and is arranged in shifting chute, wherein shifting chute exists
It is continuously formed on the length direction of moving track；The electrospinning device further includes pseudo- nozzle, and the puppet nozzle setting is moving
On dynamic rail road, with the outside for the outermost spinning-nozzle being arranged in the multiple spinning-nozzle.
According to the above technical scheme, the extrusion temperature in the step 6) is 20-80 DEG C；The spinning head specification: inner hole
For 1.3-3.4mm, exit orifice 1.4-3.6mm；The dry-spinning path temperature is 10-40 DEG C, relative humidity 30-99%RH；It is described
Setting temperature is 20-80 DEG C；The receipts silk speed is 2-10m/min.
Based on above-mentioned, it is an advantage of the current invention that having many advantages, such as that process is simple, high-efficient, while the film prepared has
Excellent corrosion-resistant, heat-resisting, cold-resistant, resistance to oxidation, weather resistance, will have selection block contaminants, prevents or reduces pollutant and exist
The irreversible deposition of film surface, improves the antifouling property of film；Solving hollow-fibre membrane, cortex is easily de- in use
The problem of falling is woven into hollow tube using the polyacrylonitrile filament with polyvinylidene fluoride surface separating layer with cosolvent characteristic
Reinforcement of the shape fabric as film, casting solution have preferable wellability to reinforcement, and reinforcement fiber gap is penetrated into part, increase
Mechanical bonding strength can reduce fracture of wire and block up a possibility that dirty, extend the service life of diaphragm.
Finally, it should be noted that being not intended to restrict the invention the foregoing is merely preferred embodiment of the invention, to the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, still can be with for the technology patient of this field
It modifies the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features.It is all
Within the spirit and principles in the present invention, any modification, equivalent replacement, improvement and so on should be included in guarantor of the invention
Within the scope of shield.
Claims (7)
1. a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film, characterized by the following steps:
1) prepare casting solution: by Kynoar, inorganic additive, pore-foaming agent, coupling agent, initiator and solvent mix after in
Ultrasonic wave disperses 30-60min at 60-80 DEG C, obtains solution；Organic additive is added in solution, stirring and dissolving, specially
8h is stirred in the 60-80 DEG C of mixing speed with 200-400r/min, then heats to 80-90 DEG C of stirring 2-5h, then cool to 70-
80 DEG C stirring 6-10 hours, through filtering and deaeration after obtain casting solution；
2) it prepares hollow braided rope: being 10% sodium hydrate aqueous solution immersion treatment with mass concentration under conditions of 30-80 DEG C
Hollow braided rope 0.5h-1h takes out washing and dries for use to remove the greasy dirt on surface；With atmospheric pressure plasma jet treatment through processed
Hollow braided rope；
3) it prepares reinforcement: being required according to properties of product, yarn needed for selecting measures negative cruvature side in reinforcement cross section
Side length combines core by the method for equivalent length of side by negative cruvature when being equivalent to positive camber and with the cross-sectional shape design after equivalent
Mould weaves reinforcement by core model of above-mentioned combination die on braider, takes out the equivalent core model in composite core formwork and makes reinforcement
It is attached on the core model not taken out, then taking out remaining core model can be obtained required reinforcement, i.e., compiles polyacrylonitrile fibre
It is made into hollow woven tube, the reinforcement as reinforced type polyvinylidene fluoride hollow fiber film；
4) it prepares primary hollow tunica fibrosa: casting solution obtained above being passed through to dry and wet spinning equipment together with core liquid and is spun
Silk is arranged on moving track wherein the electrospinning device includes: multiple moving tracks and multiple spinning-nozzles in movement
It is moved on the length direction of track；The electrospinning device further includes being integrated to the end of moving track in its longitudinal direction
Trapped orbit, wherein moving track moves in the width direction along trapped orbit；Wherein, trapped orbit has and is formed
In holding tank wherein, voltage transmission bar is inserted and secured in holding tank；Wherein, moving track is in its longitudinal direction
End contact voltage transmission pole is simultaneously integrated to trapped orbit, to cover voltage transmission bar, is prepared into primary hollow tunica fibrosa；
5) it prepares reinforcement basement membrane: primary hollow tunica fibrosa water logging will be prepared in the reinforcement and step 4) that prepare in step 3)
Bubble, and be dried after being protected hole agent processing, obtain reinforcement basement membrane；
6) hollow-fibre membrane is prepared: it is dry after reinforcement basement membrane is cleaned with neutral detergent, then with low pole organic liquid pair
It is infiltrated, and solvent and water 0-30: 70-100 are then prepared coagulation bath by mass percentage；By processed hollow volume
It knits the casting solution of rope and preparation while passing through spinning head extrusion, coagulation forming or be frozen into after first passing through the dry-spinning path of 1-15cm again
Type, then receive silk；Reinforcement basement membrane obtained is impregnated into 12-24h in 10 DEG C -40 DEG C of deionized water, to remove casting film liquid
Solvent and part pore former in system dry up to reinforced type polyvinylidene fluoride hollow fiber film.
2. a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film according to claim 1, it is characterised in that: institute
State Kynoar, inorganic additive, organic additive agent, pore-foaming agent, coupling agent, initiator, solvent and the quality for protecting hole agent
Part is Kynoar 40-50 parts, 10-15 parts of inorganic additive, 10-15 parts of organic additive, 10-15 parts of pore-foaming agent, is coupled
10-15 parts of hole agent of 5-10 parts of agent, 5-10 parts of initiator, 10-15 parts of solvent and guarantor.
3. a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film according to claim 1, it is characterised in that: institute
Stating inorganic additive is one of lithium chloride, sodium chloride, titanium chloride, titanium dioxide, silica and graphene oxide or more
The combination of kind.
4. a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film according to claim 1, it is characterised in that: institute
Stating organic additive is polyvinylpyrrolidone, polyethylene glycol, sulfonated polysulfone, polyvinyl alcohol, polyacrylonitrile and polymethyl
One of sour methyl esters or a variety of combinations.
5. a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film according to claim 1, it is characterised in that: institute
State the atmospheric pressure plasma jet treatment condition of step 2) are as follows: jet diameters 2.5cm, sprinkler height 2mm, discharge gas can be
Air, nitrogen, argon gas, oxygen, the mixture of one or both of helium, gas flow 1-20L/min, supply frequency are
5-20KHz, voltage 3-20kV, processing speed 2-10m/min.
6. a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film according to claim 1, it is characterised in that: institute
It states moving track in step 4) to be located in parallel to one another, wherein each of moving track is provided with the movement for penetrating its center
Slot, and spinning-nozzle is inserted into and is arranged in shifting chute, wherein shifting chute on the length direction of moving track continuously
It is formed；The electrospinning device further includes pseudo- nozzle, and the puppet nozzle is arranged on moving track, the multiple to be arranged on
The outside of outermost spinning-nozzle in spinning-nozzle.
7. a kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film according to claim 1, it is characterised in that: institute
Stating the extrusion temperature in step 6) is 20-80 DEG C；The spinning head specification: inner hole 1.3-3.4mm, exit orifice 1.4-3.6mm；
The dry-spinning path temperature is 10-40 DEG C, relative humidity 30-99%RH；The setting temperature is 20-80 DEG C；The receipts silk speed
Degree is 2-10m/min.
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| CN201711175301.8A CN109806777A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film |
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| CN201711175301.8A CN109806777A (en) | 2017-11-22 | 2017-11-22 | A kind of preparation method of reinforced type polyvinylidene fluoride hollow fiber film |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110238998A (en) * | 2019-07-24 | 2019-09-17 | 天津工大航泰复合材料有限公司 | A kind of flushable core model preparation method for being used in RTM forming technique and preparing hollow product |
| CN115337797A (en) * | 2022-07-08 | 2022-11-15 | 上海工程技术大学 | Method for continuously preparing polyvinylidene fluoride hollow fiber membrane |
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| CN101316647A (en) * | 2005-11-29 | 2008-12-03 | 可隆株式会社 | A braid-reinforced composite hollow fiber membrane |
| CN102512990A (en) * | 2012-01-10 | 2012-06-27 | 苏州汇龙膜技术发展有限公司 | Method for preparing internal support polyvinylidene fluoride hollow fiber membrane |
| CN103432916A (en) * | 2013-09-03 | 2013-12-11 | 天津工业大学 | Preparation method of enhanced hollow polyvinylidene fluoride fiber membrane |
| CN104117294A (en) * | 2014-08-11 | 2014-10-29 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for hydrophilia polyvinylidene fluoride hollow fiber membrane |
| WO2015146469A1 (en) * | 2014-03-26 | 2015-10-01 | 株式会社クラレ | Hollow fiber membrane, and method for producing hollow fiber membrane |
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2017
- 2017-11-22 CN CN201711175301.8A patent/CN109806777A/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101316647A (en) * | 2005-11-29 | 2008-12-03 | 可隆株式会社 | A braid-reinforced composite hollow fiber membrane |
| CN102512990A (en) * | 2012-01-10 | 2012-06-27 | 苏州汇龙膜技术发展有限公司 | Method for preparing internal support polyvinylidene fluoride hollow fiber membrane |
| CN103432916A (en) * | 2013-09-03 | 2013-12-11 | 天津工业大学 | Preparation method of enhanced hollow polyvinylidene fluoride fiber membrane |
| WO2015146469A1 (en) * | 2014-03-26 | 2015-10-01 | 株式会社クラレ | Hollow fiber membrane, and method for producing hollow fiber membrane |
| CN104117294A (en) * | 2014-08-11 | 2014-10-29 | 东莞市长安东阳光铝业研发有限公司 | Preparation method for hydrophilia polyvinylidene fluoride hollow fiber membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110238998A (en) * | 2019-07-24 | 2019-09-17 | 天津工大航泰复合材料有限公司 | A kind of flushable core model preparation method for being used in RTM forming technique and preparing hollow product |
| CN115337797A (en) * | 2022-07-08 | 2022-11-15 | 上海工程技术大学 | Method for continuously preparing polyvinylidene fluoride hollow fiber membrane |
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