CN106582323A - Preparation method of high-strength, high-throughput polyvinylidene fluoride hollow fiber membrane and product thereof - Google Patents
Preparation method of high-strength, high-throughput polyvinylidene fluoride hollow fiber membrane and product thereof Download PDFInfo
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- CN106582323A CN106582323A CN201611074344.2A CN201611074344A CN106582323A CN 106582323 A CN106582323 A CN 106582323A CN 201611074344 A CN201611074344 A CN 201611074344A CN 106582323 A CN106582323 A CN 106582323A
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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
- 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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- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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Abstract
The present invention discloses a preparation method of a high-strength, high-throughput polyvinylidene fluoride hollow fiber membrane and a product thereof. According to the preparation method, high-boiling-point mixed organic compounds capable of forming a highly-critical binary mixed diluent system at a temperature higher than 100 DEG C is employed as a diluent, and a melt spinning method is employed for preparing the porous membrane. A porous structure consisting of a support layer, an inner skin layer and an outer skin layer is liable to be prepared or formed under control by adjusting the composition and content of the binary mixed diluent, wherein the support layer is a spherical particle structure with holes on spheres and large gap between each two spheres, and the inner and outer skin layers are thin. A strict ratio of the binary mixed diluent is not demanded so that the method is simple in technique and convenient for practical production. The method has good applicability, does not need to renew equipment, is convenient to popularizepromote and shows great prospects of industrialization. The method is easy to operate, and has wild resources of materials, low costs and great application effects.
Description
Technical field
The present invention relates to material science, especially a kind of high intensity, High-flux polyvinylidene fluoride hollow fiber membrane
Preparation method and product.
Background technology
Kynoar has been widely used for because it is in the excellent properties of the aspects such as weatherability, thermostability and mechanical property
Porous film material is prepared, and is largely used to the fields such as water process, membrane contactor and medical tissue engineering.Non-solvent causes phase skill
Art and Thermal inactive technology are the common technologies for preparing perforated membrane at present.Compared with non-solvent causes phase technology, Thermal inactive
Technology has the advantages that pore structure easily regulates and controls, film dynamic performance is high, film can dry state preserve, it is especially suitable not molten at room temperature
The preparation of agent polymer porous film, using the method has prepared polyvinylidene fluoride porous film at present.
Thermal inactive technology be the inventions of Castro in 1981 (US Patent, 4247498,1981), the technology be by
Polymer forms at high temperature homogeneous phase solution with specific diluent, and when the temperature decreases, solution occurs solid-liquid or liquid-liquid phase
Separate, after extraction removing diluent, the shared space in system of diluent is formed micropore.At present Kynoar is dilute
Releasing agent mainly has two classes：There is the high boiling point organic compound of strong interaction between one and polymer, such as non-water-soluble Organic substance
Dibutyl phthalate, water miscible Organic substance such as gamma-butyrolacton.There is interaction between two and polymer general
High boiling point organic compound, such as benzophenone, diphenyl carbonate.
The ideal structure of seperation film is intensity height, the networked pore structures of insertion.Existed by force and polymer between using above-mentioned
The single high boiling point organic compound for interacting is diluent, solid-liquid split-phase can only occur and obtain crust thickness and densification (polymer
Direct crystallization is formed), supporting layer for spherical particle structure, fine and close pachydermia tunic considerably increases the filtration resistance of film, very
To so that film is almost without flux, it is impossible to meet the requirement of commercial Application.And there is phase interaction between polymer using above-mentioned
It is diluent with general single high boiling point organic compound, then liquid-liquid split-phase occurs, due to stopping in metastable region into before unstable regin
Stay the time longer, thus diluent richness phase coarsening time it is elongated and formed closing honeycomb porous structure, ultimately result in film almost
Without flux.In order to shorten the time of staying in metastable region as far as possible, generally there is the list of strong interaction between polymer
A certain amount of and diluent is added all to dissolve each other but between polymer almost without mutual at any temperature in one high boiling point organic compound
Act on and be unable to the high boiling point organic compound of thermosol polymer, form two end number mixing diluent system, make the polarity of mixed diluent
Interaction between polymer is moderate, shortens metastable regions area, i.e., in temperature-fall period during the roughening of diluent richness phase
Between shorten and form the networked pore structures of more insertion.Most typically polyvinylidene fluoride porous film is prepared in mixed diluent
" dibutyl phthalate/dioctyl phthalate " mixed diluent system (Journal of Membrane
Science 319(2008)264–270).But the very harsh (matter of such as strict measurement diluent and non-diluted agent of preparation condition
Amount ratio, temperature control precision has high demands), and masking temperature it is higher (220 DEG C, it is higher than the melt temperature of Kynoar by about 50
DEG C), at this temperature polymer is easily degraded.
The content of the invention
The purpose of the present invention is：There is provided a kind of high intensity, the preparation method of High-flux polyvinylidene fluoride hollow fiber membrane and
Product, its preparation temperature requirement to film is low, can reduce the thickness of the exodermiss of product and improve the percent opening of exodermiss, and into
The water flux of product is significantly improved, excellent in mechanical performance, to overcome the deficiencies in the prior art.
What the present invention was realized in：High intensity, the preparation method of High-flux polyvinylidene fluoride hollow fiber membrane, including such as
Lower step：
1) batch mixing pelletize：Calculate according to the mass fraction, by 20-40 parts weight average molecular weight for 10-70 ten thousand Kynoar and
After 0.1-0.5 part antioxidant is dried respectively, mixed with 55-80 part two end number mixing diluent；Mixture is squeezed
Go out pelletize, the pellet kept dry of gained is standby；Described two end number mixing diluent is by gamma-butyrolacton and hexamethylene and 1,2-
Dioctyl phthalate diisononyl esters are constituted, and the mass ratio of gamma-butyrolacton and hexamethylene and 1,2- dioctyl phthalate diisononyl esters is 10：1-4；
2) film extrusion：By step 1) in the pellet that obtains carry out spinning, spinning temperature is 140-160 DEG C, with γ-Ding Nei
, used as coelosis fluid, temperature is 60-100 DEG C, and flow velocity is 0.01-0.1L/min for ester or caprolactam；Polymer solution is through length
Spend behind the air gap for 0.5-2cm and enter in the coagulating bath being made up of deionized water, the cooling of Jing deionized waters, winding filamentation,
The primary membrane silk elder generation Jing deionized waters of gained extract water soluble organic substance, and the ethanol for being then not less than 99% with purity is extracted
Water-insoluble Organic substance, then through 120-130 DEG C of heat treatment 30-60min, that is, obtain finished product.
Step 1) described in mixing be to mix 10-20min under the conditions of 700-800rpm.
Step 1) described in mixture carried out into extruding pelletization refer to, feed the mixture into draw ratio and squeeze for 46 twin screw
Go out in machine carries out extruding pelletization in 140-170 DEG C.
Step 1) described in spinning process in winding speed be 20-30m/min.
High intensity, High-flux polyvinylidene fluoride hollow fiber membrane, it is with 20-40 parts weight average molecular weight as the poly- of 10-70 ten thousand
Vinylidene, 0.1-0.5 parts antioxidant and 55-80 part two end number mixings diluent are preparing raw material, and described two end number mixing is dilute
Agent is released by gamma-butyrolacton and hexamethylene and 1,2- dioctyl phthalate diisononyl esters composition, gamma-butyrolacton and hexamethylene and 1,2- diformazan
The mass ratio of sour diisononyl esters is 10：1-4.
The principle that the present invention is based on is as follows：(1) there is the detached temperature of solid-liquid phase less than polymer in Thermal inactive process
Melt temperature, directly crystallizes when polymer solution temperature drops to a timing polymer, using water as (industry during quenching medium
The most viable quenching medium of production), it is fast due to the polymer solution temperature rapid drawdown in place of the very strong capacity of heat transmission of water, with water quench cooling
Speed crystallization forms very thick compacted zone, selects phase separation temperature to be higher than 100 DEG C high Critical Binary Tree mixed diluent systems, due to binary
Phase separation temperature between diluent is high, therefore the separation between two end number mixing diluent is equivalent at the polymer crystallization initial stage
Raw, this aspect can hinder the growth of polymer crystallization and reduce the thickness of exodermiss, on the other hand, two end number mixing diluent
Between separation can pass through polymer formation spherical particle between and cortex at polymer cortex and improve insertion
Property.From unlike existing patent (201410726127.1, the polyolefin porous membrane with insertion honeycomb porous structure and its preparation
Method) present invention in polymer solution system need not occur liquid-liquid phase separation (phase separation temperature be higher than polymer melt temperature
Degree)；(2) feature of two end number mixing diluent system is：It is high boiling point water solublity with the good Organic substance of the Kynoar compatibility,
It is that high boiling point is non-for water-insoluble with the Organic substance of Kynoar poor compatibility.Water soluble organic substance will be between quenching medium
Generation mass transfer and make polymeric acceptor that phase separation occur while tying up to generation Thermal inactive, it is and water-insoluble organic
The presence of thing hinders the carrying out of this mass transport process, i.e. polymeric system that delayed demixing occurs and the thickness of exodermiss is further reduced
Spend and improve the percent opening of exodermiss.Due to film supporting layer and exodermiss connectivity it is good, therefore filtration resistance reduce, water flux show
Write and improve.The structure with hole is equivalent to the contact area increased between spherical particle on ball, therefore improves the mechanics of film
Performance.
Compared with prior art, the height boiling so that high Critical Binary Tree mixed diluent system can be formed higher than 100 DEG C of the invention
It (is water solublity and Kynoar phase wherein with the good Organic substance of the Kynoar compatibility that point mixing Organic substance is diluent
The bad Organic substance of capacitive is for water-insoluble), described perforated membrane is obtained using the preparation method of melt spinning, by adjusting institute
Two end number mixing diluent composition and content are stated, it is that hole and ball are carried on ball that can relatively easily obtain or control to be formed with supporting layer
Between the big spherical particle structure in space, inside and outside cortex be thin and structure of porous, although the present invention using with prior art type
Identical two end number mixing diluent, but compared with the two end number mixing diluent of prior art, it is being obtained using temperature range
Membrane structure, water solublity and mode of washing it is different, the two end number mixing diluent used in the present invention is less than polymer
Heat of solution polymer forms polymer solution during melt temperature, and polymer cooling occurs solid-liquid and is separated, extracts diluent film forming
The layer that is supported afterwards is to carry that the big spherical particle structure in space, inside and outside cortex between hole and ball be thin and structure of porous on ball,
It is separated to form supporting layer for spherical particle structure, crust thickness and fine and close right different from polymer solution Jing solid-liquids in document
Membrane structure, also different from polymer solution Jing liquid-liquid phase separation formed supporting layer for closing honeycomb porous structure or patent in
The honeycomb of the insertion that (201410726127.1, polyolefin porous membrane with insertion honeycomb porous structure and preparation method thereof) refer to
Pore structure.In addition, being water solublity with the good Organic substance of the Kynoar compatibility, bad with the Kynoar compatibility is organic
Thing is water-insoluble.First water soluble organic substance extracted using deionized water during extracting and washing, be then not less than 99% with purity
Ethanol extract water-insoluble Organic substance.Because it does not require the strict proportioning of two end number mixing diluent, thus process is simple, just
In actual production.Adaptability is good, it is not necessary to more new equipment, is easy to promote, with good industrial prospect.It is of the invention simple easy
Row, material source are extensive, with low cost, and using effect is good.
Description of the drawings
Accompanying drawing 1 is Jing solid-liquid split-phases in document Journal of Membrane Science 319 (2008) 264-270
The structure of the densification thickness exodermiss for obtaining；
There is the structure in hole on the exodermiss that accompanying drawing 2 is obtained for the present invention.
Specific embodiment
Embodiments of the invention 1：High intensity, the preparation method of High-flux polyvinylidene fluoride hollow fiber membrane
1) batch mixing pelletize：Calculate according to the mass fraction, by 20 parts of Kynoar (weight average molecular weight is 700,000), 0.1 part resists
After oxygen agent is dried respectively, (gamma-butyrolacton and hexamethylene 1,2- dioctyl phthalate two are consisted of with 79.9 parts of two end number mixing diluent
Isononyl ester, both mass ratioes be 10/1) in high mixer with 800rpm under the conditions of mix 10min, add draw ratio to be 46 pairs
Extruding pelletization is carried out in 140 DEG C in screw extruder, the pellet kept dry of gained is standby；
2) film extrusion：By step 1) in the pellet that obtains carry out spinning with single screw rod, spinning temperature is 140 DEG C, with γ-
Butyrolactone is 60 DEG C as coelosis fluid, temperature, and flow velocity is 0.1L/min；Polymer solution through length for 0.5cm air
The cooling of Jing deionized waters, winding filamentation are entered behind gap, winding speed is 30m/min in spinning process；The primary membrane silk of gained
First Jing deionized waters extract water soluble organic substance then the ethanol that is not less than 99% with purity extract it is water-insoluble organic
Thing, then through 130 DEG C of heat treatment 60min, you can obtain high intensity, high-throughout Pvdf Microporous Hollow Fiber Membrane.
Jing is determined, and the film that embodiment 1 is obtained is that the big spherical particle structure in space between hole and ball, inside and outside is carried on ball
The thin structure of cortex, fracture strength 7.0MPa, elongation at break is 90%, at 0.1MPa and 25 DEG C, the doughnut of gained
The pure water flux of perforated membrane is 1200 (L/m2/h)。
Embodiment 2：High intensity, the preparation method of High-flux polyvinylidene fluoride hollow fiber membrane,
1) batch mixing pelletize：Calculate according to the mass fraction, by 40 parts of Kynoar (weight average molecular weight is 100,000), 0.5 part resists
After oxygen agent is dried respectively, with 59.5 parts of two end number mixing diluent (consist of caprolactam and DOTP, two
Person's mass ratio be 10/4) in high mixer with 800rpm under the conditions of mix 20min, add draw ratio to be in 46 double screw extruders
Extruding pelletization is carried out in 170 DEG C, the pellet kept dry of gained is standby；
2) film extrusion：By step 1) in the pellet that obtains carry out spinning with single screw rod, spinning temperature is 140 DEG C, with oneself
Lactams are 80 DEG C as coelosis fluid, temperature, and flow velocity is 0.01L/min；Polymer solution is through between air of the length for 1cm
The cooling of Jing deionized waters, winding filamentation are entered after gap, winding speed is 20m/min in spinning process；The primary membrane silk elder generation of gained
Jing deionized waters extract water soluble organic substance and then the ethanol that is not less than 99% with purity extracts water-insoluble Organic substance,
Again through 130 DEG C of heat treatment 40min, you can obtain high intensity, high-throughout Pvdf Microporous Hollow Fiber Membrane.
Jing is determined, and the film that embodiment 2 is obtained is that the big spherical particle structure in space between hole and ball, inside and outside is carried on ball
The thin structure of cortex, fracture strength 15.0MPa, elongation at break is 120%, at 0.1MPa and 25 DEG C, the hollow fibre of gained
The pure water flux of dimension perforated membrane is 900 (L/m2/h)。
Embodiment 3：High intensity, the preparation method of High-flux polyvinylidene fluoride hollow fiber membrane,
1) batch mixing pelletize：Calculate according to the mass fraction, by 30 parts of Kynoar (weight average molecular weight is 500,000), 0.5 part resists
After oxygen agent is dried respectively, with 69.5 parts of two end number mixing diluent (consist of ethylene carbonate and the hard ester of glycol monoethyl ether,
Both mass ratioes be 10/2) in high mixer with 700rpm under the conditions of mix 20min, additions draw ratio is 46 double screw extruders
In carry out extruding pelletization in 160 DEG C, the pellet kept dry of gained is standby；
2) film extrusion：By step 1) in the pellet that obtains carry out spinning with single screw rod, spinning temperature is 160 DEG C, with oneself
Lactams are 100 DEG C as coelosis fluid, temperature, and flow velocity is 0.05L/min；Polymer solution through length for 2cm air
The cooling of Jing deionized waters, winding filamentation are entered behind gap, winding speed is 20m/min in spinning process；The primary membrane silk of gained
First Jing deionized waters extract water soluble organic substance then the ethanol that is not less than 99% with purity extract it is water-insoluble organic
Thing, then through 120 DEG C of heat treatment 30min, you can obtain high intensity, high-throughout Pvdf Microporous Hollow Fiber Membrane.
Jing is determined, and the film that embodiment 3 is obtained is that the big spherical particle structure in space between hole and ball, inside and outside is carried on ball
The thin structure of cortex, fracture strength 12.0MPa, elongation at break is 130%, at 0.1MPa and 25 DEG C, the hollow fibre of gained
The pure water flux of dimension perforated membrane is 920 (L/m2/h)。
Embodiment 4：High intensity, the preparation method of High-flux polyvinylidene fluoride hollow fiber membrane,
1) batch mixing pelletize：Calculate according to the mass fraction, by 30 parts of Kynoar (weight average molecular weight is 700,000), 0.1 part resists
After oxygen agent is dried respectively, with 79.9 parts of two end number mixing diluent (consist of gamma-butyrolacton and the hard ester of glycol monoethyl ether,
Both mass ratioes be 10/3) in high mixer with 800rpm under the conditions of mix 10min, additions draw ratio is 46 double screw extruders
In carry out extruding pelletization in 150 DEG C, the pellet kept dry of gained is standby；
2) film extrusion：By step 1) in the pellet that obtains carry out spinning with single screw rod, spinning temperature is 150 DEG C, with γ-
Butyrolactone is 60 DEG C as coelosis fluid, temperature, and flow velocity is 0.1L/min；Polymer solution is through between air of the length for 1cm
The cooling of Jing deionized waters, winding filamentation are entered after gap, winding speed is 30m/min in spinning process；The primary membrane silk elder generation of gained
Water soluble organic substance is extracted Jing deionized water and then be not less than with purity water-insoluble organic after 99% ethanol is extracted
Thing, then through 130 DEG C of heat treatment 60min, you can obtain high intensity, high-throughout Pvdf Microporous Hollow Fiber Membrane.
Jing is determined, and the film that embodiment 4 is obtained is that the big spherical particle structure in space between hole and ball, inside and outside is carried on ball
The thin structure of cortex, fracture strength 13.0MPa, elongation at break is 115%, at 0.1MPa and 25 DEG C, the hollow fibre of gained
The pure water flux of dimension perforated membrane is 1030 (L/m2/h)。
Claims (5)
1. a kind of high intensity, the preparation method of High-flux polyvinylidene fluoride hollow fiber membrane, it is characterised in that including following step
Suddenly：
1) batch mixing pelletize：Calculate according to the mass fraction, by Kynoar and 0.1- that 20-40 parts weight average molecular weight is 10-70 ten thousand
After 0.5 part of antioxidant is dried respectively, mixed with 55-80 part two end number mixing diluent；Mixture is carried out into extrusion to make
Grain, the pellet kept dry of gained is standby；Described two end number mixing diluent is by gamma-butyrolacton and hexamethylene and 1,2- diformazan
The mass ratio of sour diisononyl esters composition, gamma-butyrolacton and hexamethylene and 1,2- dioctyl phthalate diisononyl esters is 10：1-4；
2) film extrusion：By step 1) in the pellet that obtains carry out spinning, spinning temperature is 140-160 DEG C, with gamma-butyrolacton or
Caprolactam is 60-100 DEG C as coelosis fluid, temperature, and flow velocity is 0.01-0.1L/min；Polymer solution is through length
Enter behind the air gap of 0.5-2cm in coagulating bath, the cooling of Jing deionized waters, winding filamentation, the primary membrane silk elder generation Jing of gained goes
Ionized water extracts water soluble organic substance, and the ethanol for being then not less than 99% with purity extracts water-insoluble Organic substance, then Jing
120-130 DEG C of heat treatment 30-60min is crossed, that is, obtains finished product.
2. preparation method according to claim 1, it is characterised in that：Step 1) described in mixing be, in 700-
Mix 10-20min under the conditions of 800rpm.
3. preparation method according to claim 1, it is characterised in that：Step 1) described in mixture carried out into extrusion make
Grain refers to that it is to carry out extruding pelletization in 140-170 DEG C in 46 double screw extruders to feed the mixture into draw ratio.
4. preparation method according to claim 1, it is characterised in that：Step 1) described in spinning process in winding speed
For 20-30m/min.
5. the preparation method described in a kind of employing claim 1 is obtained high intensity, High-flux polyvinylidene fluoride hollow fiber membrane,
It is characterized in that：It is with 20-40 parts weight average molecular weight as the Kynoar of 10-70 ten thousand, 0.1-0.5 parts antioxidant and 55-
80 parts of two end number mixing diluent are preparing raw material, and described two end number mixing diluent is by gamma-butyrolacton and hexamethylene and 1,2- bis-
Formic acid diisononyl esters are constituted, and the mass ratio of gamma-butyrolacton and hexamethylene and 1,2- dioctyl phthalate diisononyl esters is 10：1-4.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107297155A (en) * | 2017-07-05 | 2017-10-27 | 贵州省材料产业技术研究院 | The preparation method of superhigh intensity polypropylene hollow fiber membrane |
| CN110721598A (en) * | 2019-09-27 | 2020-01-24 | 贵州省材料产业技术研究院 | Preparation method of high-flux porous membrane |
| CN110721597A (en) * | 2019-09-27 | 2020-01-24 | 贵州省材料产业技术研究院 | Method for simply preparing porous membrane with excellent connectivity |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439268A (en) * | 2008-12-09 | 2009-05-27 | 南京龙源环保有限公司 | Method for preparing high-intensity high-throughput polyvinylidene fluoride hollow fiber membrane |
| CN101507902A (en) * | 2009-02-19 | 2009-08-19 | 苏州膜华材料科技有限公司 | Preparation method of porous polyvinylidene fluoride alloy membrane for treating and recycling waste water |
| JP2012196618A (en) * | 2011-03-22 | 2012-10-18 | Sumitomo Electric Ind Ltd | Filtration membrane, and membrane filtration method and device |
| CN102764597A (en) * | 2012-08-01 | 2012-11-07 | 清华大学 | Method for preparing polyvinylidene fluoride ultra-filtration membranes |
| CN104474921A (en) * | 2014-12-04 | 2015-04-01 | 贵州省材料产业技术研究院 | Polyolefin porous membrane with perforated honeycomb pore structure and preparation method thereof |
-
2016
- 2016-11-29 CN CN201611074344.2A patent/CN106582323B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101439268A (en) * | 2008-12-09 | 2009-05-27 | 南京龙源环保有限公司 | Method for preparing high-intensity high-throughput polyvinylidene fluoride hollow fiber membrane |
| CN101507902A (en) * | 2009-02-19 | 2009-08-19 | 苏州膜华材料科技有限公司 | Preparation method of porous polyvinylidene fluoride alloy membrane for treating and recycling waste water |
| JP2012196618A (en) * | 2011-03-22 | 2012-10-18 | Sumitomo Electric Ind Ltd | Filtration membrane, and membrane filtration method and device |
| CN102764597A (en) * | 2012-08-01 | 2012-11-07 | 清华大学 | Method for preparing polyvinylidene fluoride ultra-filtration membranes |
| CN104474921A (en) * | 2014-12-04 | 2015-04-01 | 贵州省材料产业技术研究院 | Polyolefin porous membrane with perforated honeycomb pore structure and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 楼紫阳等: "《渗滤液处理处置技术及工程实例》", 31 January 2007, 北京：化学工业出版社 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107297155A (en) * | 2017-07-05 | 2017-10-27 | 贵州省材料产业技术研究院 | The preparation method of superhigh intensity polypropylene hollow fiber membrane |
| CN110721598A (en) * | 2019-09-27 | 2020-01-24 | 贵州省材料产业技术研究院 | Preparation method of high-flux porous membrane |
| CN110721597A (en) * | 2019-09-27 | 2020-01-24 | 贵州省材料产业技术研究院 | Method for simply preparing porous membrane with excellent connectivity |
| CN110721597B (en) * | 2019-09-27 | 2022-03-29 | 贵州省材料产业技术研究院 | Method for simply preparing porous membrane with excellent connectivity |
| CN110721598B (en) * | 2019-09-27 | 2022-03-29 | 贵州省材料产业技术研究院 | Preparation method of high-flux porous membrane |
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