CN106731904A - The preparation method of unilateral super-hydrophobic poly (ether sulfone) film - Google Patents
The preparation method of unilateral super-hydrophobic poly (ether sulfone) film Download PDFInfo
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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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
- B01D2325/38—Hydrophobic membranes
Abstract
The invention discloses a kind of preparation method of unilateral super-hydrophobic poly (ether sulfone) film, the method is to dissolve in a solvent polyether sulfone, poly (ether sulfone) film is prepared by wet-dry change, then Silicon dioxide sol-gel is prepared by sol-gal process, and Silicon dioxide sol-gel is modified with fluorine containing silane, prepare the Silicon dioxide sol-gel filtered fluid of fluorination, the Silicon dioxide sol-gel of fluorination is deposited to using the method for vacuum filtration for the side of poly (ether sulfone) film, the unilateral poly (ether sulfone) film with ultra-hydrophobicity is obtained.The method is mainly used in requirement has the UF membrane field of unilateral hydrophobic performance, can be used for film absorption, film parsing and the preparation of gas-liquid membrane contactor method nano material.The method is simple, easily operated, and obtained film hydrophobicity is good and preparation cost is greatly lowered.
Description
Technical field
The invention belongs to separate technical field of membrane, and in particular to a kind of preparation method of unilateral super-hydrophobic poly (ether sulfone) film.
Background technology
Solution-air membrane contactor technology with its gas-liquid mass transfer interface stability, specific surface area high, small volume, modularization, be easy to
The amplification and diminution of scale, can with the flow velocity of independent control gas and liquid the advantages of, new membrane technology is rapidly become, in film
Absorb, film parsing, Membrane Materials it is gentle-liquid membrane contactor prepare nano material aspect obtained it is widely studied and application, cause phase
The extensive concern of Guan researcher.In the research and application of solution-air membrane contactor technology, the hydrophobic performance of membrane material is to determine
The key of membrane contactor success application.Absorbed with film resolving in film, solution-air membrane contactor divides gas phase and liquid phase
Separate, solution-air membrane contactor merely provides the contact interface of gas-liquid two-phase, connecing for gas-liquid two-phase is formed at each fenestra mouth
Interface is touched, therefore, the film for solution-air membrane contactor only has side to be contacted with liquid, and that side contacted with liquid needs tool
There is good hydrophobic performance.
Chinese invention patent publication number CN 103386261A disclose a kind of super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane
Preparation method, polytetrafluoroethyldispersion dispersion resin powder is mixed with extrusion aid, pressed compact, and blank is extruded into gathering by pushing machine
Tetrafluoroethene hollow tube, then after Ludox is modified treatment to polytetrafluoroethylene (PTFE) hollow tube, then is carried out in an oven
Longitudinal stretching and sintering thermal finalization, finally, infiltration treatment are carried out using perfluor silane, obtain the hollow fibre of super-hydrophobic polytetrafluoroethylene (PTFE)
Dimension film.This patent provide prepare super-hydrophobic polytetrafluoroethylhollow hollow fiber membrane technique it is cumbersome, it is necessary to mix, pressed compact, extruding
The steps such as shaping, Ludox treatment, stretching, thermal finalization and perfluor silane treatment；Pushing machine, stretching and sintering etc. is needed large-scale to set
It is standby；Due to polytetrafluoroethylmaterial material hydrophobic membrane inherently high, the raising of hydrophobic performance is not apparent；Additionally, this technique
The permeability of the polytetrafluoroethylhollow hollow fiber membrane of production is poor.
The A of Chinese invention patent publication number CN 103285746 disclose a kind of for going the super of dissolved gas in water removal
The preparation method of hydrophobic membrane, the inorganic nano-particle and hydrophobic macromolecule with low-surface-energy that will be modified through coupling agent
After PVDF blendings, a kind of super-hydrophobic film for removing dissolved gas in water removal is prepared using phase inversion, it is super thin in order to obtain
Water film surface, in this technique, the inorganic nano-particle major part with low-surface-energy of coupling agent modification is both dispersed in film
Portion, because the price with low-surface energy substance is super-hydrophobic solution-air for only needing with liquid contacting side costly
Membrane contactor film, the preparation method of this super-hydrophobic film has certain waste.
Chinese invention patent publication number CN101463140 A disclose a kind of preparation method of ultra-hydrophobic polyvinylidene fluoride membrane
And its product, it carries out hydrophobic changing after pvdf membrane is carried out into corona treatment by chemistry or chemical vapor deposition organosilan
Property, super-hydrophobic pvdf membrane is obtained, the bilateral of pvdf membrane prepared by this technique all has hydrophobic performance, due to fluorine containing silane price
Costly, there is certain waste for the film for needing unilateral hydrophobic performance, additionally, this technique needs specific plasma to set
It is standby, it is necessary to the equipment investment of early stage, preparation cost is higher.
The content of the invention
It is relatively low, good permeability unilateral super-hydrophobic poly (ether sulfone) film it is an object of the invention to provide a kind of easy to operate, cost
Preparation method.
Therefore, technical scheme is as follows：
A kind of preparation method of unilateral super-hydrophobic poly (ether sulfone) film, comprises the following steps：
(1) preparation of poly (ether sulfone) film：The DMA of mass fraction 70%-90% is added to there-necked flask
In, it is the polyethylene glycol of 1-10% for the polyether sulfone and mass fraction of 10-20% to add mass fraction, is stirred at 50-80 DEG C
5-8h, after polymer is completely dissolved, carries out ultrasonic deaeration, obtains casting solution；The casting solution scraper is scraped on a glass
Film is made, curing molding in coagulating bath is then immersed in, then is soaked film 3-5 days with deionized water, wet film is dried afterwards
Treatment, obtains poly (ether sulfone) film；
(2) preparation of fluorided silica silica sol gel filtered fluid：Absolute ethyl alcohol is added in three mouthfuls of clean beakers, so
It is the ammoniacal liquor of 25wt% that concentration is added dropwise in backward three mouthfuls of beakers, and at least 30min is stirred at 60-80 DEG C, makes it uniform mixed
Close, then side continues to stir at least 3h to tetraethyl orthosilicate is added dropwise in three mouthfuls of beakers, obtains uniform milky sol solutionses,
The sol solutionses are poured into beaker, still aging 24h；Then, perfluoro decyl triethoxysilane is added into above-mentioned sol solutionses
In, at least 3h is stirred at 60 DEG C, fluorided silica silica sol gel filtered fluid is obtained, wherein, the absolute ethyl alcohol, concentration are
The ammoniacal liquor of 25wt% and the mol ratio of tetraethyl orthosilicate are 50:(1-3):(1-3), the perfluoro decyl triethoxysilane with just
The mol ratio of silester is 1-4:1；
(3) preparation of unilateral super-hydrophobic poly (ether sulfone) film：Poly (ether sulfone) film obtained in step (1) is cut into a diameter of 120mm's
Circle, is put into the Buchner funnel of a diameter of 120mm；By fluorinated silica sol gel solution obtained in 5-30ml steps (2)
It is poured on the poly (ether sulfone) film surface for treating suction filtration, suction filtration, until the fluorinated silica sol gel solution suction filtration on poly (ether sulfone) film surface
Completely；Poly (ether sulfone) film after suction filtration is placed in baking oven, 1-60min is heat-treated at 60-100 DEG C, obtain the one side super-hydrophobic
Poly (ether sulfone) film.
In above-mentioned steps (1), treatment is dried to the wet film using liquid displacement desiccation method；The coagulating bath is
Water.
In above-mentioned steps (3), suction filtration is carried out under 0.02-0.06MPa with circulating water type vavuum pump.
The method of the present invention is mainly used in requirement has the UF membrane field of unilateral hydrophobic performance, for film absorption, film solution
Analyse the preparation of gentle-liquid membrane contactor method nano material.Compared with prior art, the invention has the advantages that：
(1) this law prepares Silicon dioxide sol-gel using sol-gel technique, by fluorinated modified treatment, in dioxy
SiClx collosol and gel surface grafting perfluoro decyl triethoxysilane, fluorinated modified, the silica of formation fluorination is carried out to it
Collosol and gel filtered fluid, then by simple, easily operated vacuum filtration method, the silica micro-and nano-particles that will be fluorinated are uniform
Be deposited on PES film single side surfaces, unilateral super-hydrophobic PES films are formed, so as to realize super-hydrophobicization of unilateral PES films.Additionally,
This preparation method for preparing super-hydrophobic film is one layer of modified layer of formation very thin (micron order) in film, and modified layer is by nanometer
The particle packing of level is formed, and has gap between nano particle, therefore, the preparation of this super-hydrophobic film not to its it is original compared with
Permeability high produces considerable influence.
(2) this law is based on the preparation technology and equipment of existing unilateral super-hydrophobic poly (ether sulfone) film, and material surface can reach super thin
Water needs two necessary conditions：Surface roughness high and the surface with low-surface-energy, it is most of in existing invention
The preparation method for preparing super-hydrophobic film is mainly completed by the structure of rough surface high and modification two parts of low-surface-energy, this hair
Bright method combines this two parts, first prepares the nano silicon dioxide sol modified by low-surface-energy fluoride and filters
Liquid, then by simple physical vacuum suction filtration finished product.Because the preparation of this super-hydrophobic film pertains only to filtered fluid and prepares and take out
Two technical process of filter, therefore, it is this inventive method process is simple, easily operated；Because this Fang Ming need not add extras,
So, there is no the input of early stage equipment, cost is relatively low；Due to the existing price with low-surface energy substance all costly,
It is that super-hydrophobic solution-air film connects for only needing with liquid contacting side and this material is the indispensable material for preparing super-hydrophobic film
Tentaculum film, the inventive method only needs the less surface energy substance to have carried out the raising of hydrophobic performance in certain films side, because
This, preparation cost is greatly lowered, with great practical value.
Specific embodiment
The preparation method of unilateral super-hydrophobic poly (ether sulfone) film of the invention, is to dissolve in a solvent, by dry and wet polyether sulfone
Method prepares PES films, then, Silicon dioxide sol-gel is prepared by sol-gal process, and molten to silica with fluorine containing silane
Glue gel is modified, and prepares the Silicon dioxide sol-gel filtered fluid of fluorination, two will be fluorinated using the method for vacuum filtration
Silica sol gel deposits to the side of PES films, prepares the unilateral poly (ether sulfone) film with ultra-hydrophobicity.
Preparation method of the invention is described further with reference to instantiation.
Embodiment 1
(1) preparation of poly (ether sulfone) film：By dried PES powder and DMAc in mass ratio 17：83 mixing, in band heating
7h is slowly stirred in magnetic stirring apparatus, and by casting solution temperature control at 65 DEG C, after polymer is completely dissolved, carries out ultrasound de-
Bubble, obtains casting solution.At ambient temperature, by casting solution evenly and rapidly knifing on a glass, then Yu Shuizhong utilizes phase
Conversion method film forming, after being soaked 3.5 days in coagulating bath deionized water, cleaning is dried, and obtains poly (ether sulfone) film.This PES film air flux
It is 199.8m3/m2H, contact angle is 78 ゜ (contact angle is less than 90 ゜, is hydrophilic film).
(2) preparation of fluorided silica silica sol gel filtered fluid：It is the ammoniacal liquor and just of 25wt% by absolute ethyl alcohol, concentration
The mol ratio of silester (TEOS) is 50:1:1, ethanol is added in three mouthfuls of clean beakers, and ammoniacal liquor is added dropwise in proportion,
35min is stirred at 80 DEG C, after making its uniform mixing, to tetraethyl orthosilicate is added dropwise in there-necked flask in proportion, continues to stir 3h, obtained
To the uniform sol solutionses of milky, the sol solutionses are poured into beaker, still aging 24h；Then, by perfluoro decyl triethoxy
Silane (PFDTES) adds above-mentioned sol gel solution, and 3h is stirred at 60 DEG C, obtains fluorided silica silica sol gel filtered fluid.
Wherein, the mol ratio of PFDTES and TEOS is 1:1.
(3) preparation of unilateral super-hydrophobic poly (ether sulfone) film：Poly (ether sulfone) film obtained in step (1) is cut into a diameter of 120mm's
Circle, is put into the Buchner funnel of a diameter of 120mm；Fluorinated silica sol gel solution obtained in 5ml steps (2) is poured into
The PES films surface (air side) of suction filtration is treated, suction filtration is carried out under 0.02MPa with circulating water type vavuum pump, until PES films surface
Fluorinated silica sol gel solution suction filtration is complete；PES films after suction filtration are placed in baking oven and are heat-treated 0.5h in the case of 95 DEG C,
Obtain the unilateral super-hydrophobic poly (ether sulfone) film.The air flux of the film is 197.4m3/m2H, contact angle is that (contact angle is more than 119 ゜
90 ゜, are hydrophilic film).
Embodiment 2
(1) preparation of poly (ether sulfone) film：In mass ratio it is 10 by dried PES powder, PEG400 and DMAc:10:80 mix
Close, on the magnetic stirring apparatus of band heating, be slowly stirred 6 hours, make film liquid temperature control at 60 DEG C, obtain the casting uniformly clarified
Film liquid, and by casting solution temperature control at 60 DEG C, ultrasonic deaeration is carried out, obtain casting solution.At ambient temperature, it is casting solution is equal
Even quickly knifing on a glass, then Yu Shuizhong utilize forming film with phase transformation method, after being soaked 4 days in deionized water, cleaning,
Dry, obtain poly (ether sulfone) film.
(2) preparation of fluorided silica silica sol gel filtered fluid：Absolute ethyl alcohol, 25% ammoniacal liquor and tetraethyl orthosilicate
(TEOS) adding proportion is 50:1:3, ethanol is added in three mouthfuls of clean beakers, and ammoniacal liquor is added dropwise in proportion, at 70 DEG C
After stirring 45min makes its uniform mixing, to tetraethyl orthosilicate is added dropwise in there-necked flask in proportion, continue to stir 5h, obtain milky white
The uniform sol solutionses of color, the sol solutionses are poured into beaker, still aging 24h is standby；Then, by perfluoro decyl triethoxy
Silane (PFDTES) is added to above-mentioned sol gel solution, and 3.5h is stirred at 60 DEG C, obtains fluorided silica silica sol gel mistake
Filtrate.The mol ratio of wherein PFDTES and TEOS is 1:1.
(3) preparation of unilateral super-hydrophobic poly (ether sulfone) film：Film obtained in step (1) is cut into the circle of a diameter of 120mm, is put
In entering the Buchner funnel of a diameter of 120mm；5ml fluorinated silica sol gel solutions are poured into and treats that the PES films surface of suction filtration is (empty
Gas side), suction filtration is carried out under 0.03MPa with circulating water type vavuum pump, until the fluorided silica silica sol gel on PES films surface
Liquid suction filtration is complete；PES films are placed in baking oven, 1h is heat-treated at 80 DEG C, obtain the unilateral super-hydrophobic poly (ether sulfone) film.The film
Air flux is 212.7m3/m2H, contact angle is 122 ゜.
Embodiment 3
(1) preparation of poly (ether sulfone) film：By dried PES powder, PEG400 and DMAc in mass ratio 15:5:80 mixing,
On the magnetic stirring apparatus of band heating, it is slowly stirred 7.5 hours, makes film liquid temperature control at 80 DEG C, obtains the casting uniformly clarified
Film liquid, and by casting solution temperature control at 80 DEG C, ultrasonic deaeration is carried out, obtain casting solution.At ambient temperature, by casting solution point
Evenly and rapidly knifing on a glass, does not then utilize forming film with phase transformation method, in coagulating bath (water) in coagulating bath (water)
After immersion 4.5 days, cleaning is dried.
(2) preparation of fluorided silica silica sol gel filtered fluid：Absolute ethyl alcohol, 25% ammoniacal liquor and tetraethyl orthosilicate
(TEOS) adding proportion is 50:1:3, ethanol is added in three mouthfuls of clean beakers, and ammoniacal liquor is added dropwise in proportion, at 75 DEG C
After stirring 50min makes its uniform mixing, to tetraethyl orthosilicate is added dropwise in there-necked flask in proportion, continue to stir 4h, obtain milky white
The uniform sol solutionses of color, the sol solutionses are poured into beaker, and still aging 24h is standby；Then, by perfluoro decyl triethoxysilicane
Alkane (PFDTES) according to material the ratio between amount PFDTES：TEOS is 1:4 are added to above-mentioned sol gel solution, are stirred at 60 DEG C
5h, obtains fluorided silica silica sol gel filtered fluid.
(3) preparation of unilateral super-hydrophobic poly (ether sulfone) film：Film is cut into the circle of a diameter of 120mm, a diameter of 120mm is put into
Buchner funnel in；30ml fluorinated silica sol gel solutions are poured into the PES films surface (air side) for treating suction filtration, with circulation
Ability of swimming vavuum pump carries out suction filtration under 0.05MPa, until the fluorinated silica sol gel solution suction filtration on PES films surface is complete；
PES films are placed in baking oven, 60min is heat-treated at 80 DEG C, obtain the unilateral super-hydrophobic poly (ether sulfone) film.The air flux of the film is
179.6m3/m2H, contact angle is 150.2 ゜, has reached super-hydrophobic requirement.
Table 1 list unilateral super-hydrophobic poly (ether sulfone) film obtained in 3 embodiments of the invention and PES original film Air permenbility and
The indicated value of contact angle：
Table 1
| Film type | Air permenbility/m3/m2H (under 10kPa) | Contact angle/゜ |
| PES original films | 199.8 | 78 |
| Embodiment 1 | 197.4 | 119 |
| Embodiment 2 | 192.7 | 122 |
| Embodiment 3 | 179.6 | 150.2 |
From parameter value in table 1, the contact angle of PES films is respectively 119 ゜, 122 ゜ obtained in 3 embodiments of the invention
With 150.2 ゜, and the contact angle of PES films be 78 ゜；The air flux of PES films is respectively obtained in 3 embodiments of the invention
197.4m3/m2h, 192.7m3/m2h and 179.6m3/m2h, and PES films air flux is 199.8m3/m2h, can be with
More clearly find out, the fluorinated nano silica dioxide granule of deposition on the premise of without the excellent air permeability for changing PES films,
The hydrophobic performance of PES films is considerably improved, the contact angle of PES films brings up to 150.2, reached super from 78 ゜ of PES original films
Hydrophobic requirement.
Claims (4)
1. a kind of preparation method of unilateral super-hydrophobic poly (ether sulfone) film, it is characterised in that comprise the following steps：
(1) preparation of poly (ether sulfone) film：The DMA of mass fraction 70%-90% is added in there-necked flask,
It is the polyethylene glycol of 1-10% for the polyether sulfone and mass fraction of 10-20% to add mass fraction, and 5- is stirred at 50-80 DEG C
8h, after polymer is completely dissolved, carries out ultrasonic deaeration, obtains casting solution；By casting solution scraper striking on a glass
Film forming, is then immersed in curing molding in coagulating bath, then is soaked film 3-5 days with deionized water, is dried place to wet film afterwards
Reason, obtains poly (ether sulfone) film；
(2) preparation of fluorided silica silica sol gel filtered fluid：Absolute ethyl alcohol, Ran Houxiang are added in three mouthfuls of clean beakers
It is the ammoniacal liquor of 25wt% that concentration is added dropwise in three mouthfuls of beakers, and at least 30min is stirred at 60-80 DEG C, makes its uniform mixing, so
Back continues to stir at least 3h to tetraethyl orthosilicate is added dropwise in three mouthfuls of beakers, obtains uniform milky sol solutionses, will be described
Sol solutionses are poured into beaker, still aging 24h；Then, in perfluoro decyl triethoxysilane being added into above-mentioned sol solutionses, 60
At least 3h is stirred at DEG C, fluorided silica silica sol gel filtered fluid is obtained, wherein, the absolute ethyl alcohol, concentration are 25wt%
Ammoniacal liquor and tetraethyl orthosilicate mol ratio be 50:(1-3):(1-3), the perfluoro decyl triethoxysilane and positive silicic acid second
The mol ratio of ester is 1-4:1；
(3) preparation of unilateral super-hydrophobic poly (ether sulfone) film：Poly (ether sulfone) film obtained in step (1) is cut into the circle of a diameter of 120mm,
It is put into the Buchner funnel of a diameter of 120mm；Fluorinated silica sol gel solution obtained in 5-30ml steps (2) is poured on and is treated
On the poly (ether sulfone) film surface of suction filtration, suction filtration, until the fluorinated silica sol gel solution suction filtration on poly (ether sulfone) film surface is complete；Will
Poly (ether sulfone) film after suction filtration is placed in baking oven, and 1-60min is heat-treated at 60-100 DEG C, obtains the unilateral super-hydrophobic polyether sulfone
Film.
2. preparation method according to claim 1, it is characterised in that：In step (1), using liquid displacement desiccation method to institute
State wet film and be dried treatment.
3. preparation method according to claim 1, it is characterised in that：In step (1), the coagulating bath is water.
4. preparation method according to claim 1, it is characterised in that：In step (3), existed with circulating water type vavuum pump
Suction filtration is carried out under 0.02-0.06MPa.
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| CN109267330A (en) * | 2018-10-26 | 2019-01-25 | 南京科技职业学院 | A kind of oleophobic method of modifying of polybutadiene film |
| CN110237727A (en) * | 2019-06-19 | 2019-09-17 | 中国科学技术大学 | A kind of preparation method of super-hydrophobic seperation film |
| CN110237727B (en) * | 2019-06-19 | 2021-04-23 | 中国科学技术大学 | Preparation method of super-hydrophobic separation membrane |
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| CN113171689A (en) * | 2021-04-27 | 2021-07-27 | 东北电力大学 | Membrane preparation method combining nano particles with membrane surface microstructure construction |
| CN113171689B (en) * | 2021-04-27 | 2022-05-10 | 东北电力大学 | Membrane preparation method combining nano particles with membrane surface microstructure construction |
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