CN110052177A - A kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane - Google Patents
A kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane Download PDFInfo
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- CN110052177A CN110052177A CN201910269986.5A CN201910269986A CN110052177A CN 110052177 A CN110052177 A CN 110052177A CN 201910269986 A CN201910269986 A CN 201910269986A CN 110052177 A CN110052177 A CN 110052177A
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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
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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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
Abstract
Surface is compacted zone in the structure of conventional polymer filter membrane, and inside contains a large amount of finger-like pores, strongly to avoid introducing bubble in casting solution in preparation process, because the bubble in film surface compacted zone will lead to film leakage.Using solder(ing)acid as solvent, water is that coagulating bath can prepare the polyacrylonitrile homogeneous membrane without finger-like pore.For the flux for further increasing film, the present invention is by the silane-modified hollow silica microsphere containing double bond functional group, double bond is introduced on hollow silica microsphere surface, and this microballoon is dispersed in solder(ing)acid, then acrylonitrile monemer, the second comonomer and initiator is added, cause Raolical polymerizable under stiring, obtains polyacrylonitrile-second comonomer copolymer casting solution of hollow silica microsphere grafting.Preparing hollow microsphere as coagulating bath using water enhances high pass weight polyacrylonitrile filter membrane.The film retains height to dyestuff, and low to inorganic salts retention, has broad application prospects in dye desalination purification art.
Description
Technical field
The present invention relates to a kind of preparation methods of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane, belong to functional material
With UF membrane field.
The present invention relates to the technical fields such as polyacrylonitrile, filter membrane, polymerization reaction, hollow silica microsphere.Specifically relate to
And a kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane, and its in dye wastewater treatment and dye desalination
In application.
Background technique
Dyeing waste water due to its toxicity, high salinity and coloration become water pollution the main reason for one of [water treatment technology,
2008,34 (3): 48-48].The direct emission of dyeing waste water can have a negative impact to water ecosystem, and waste largely has
The dyestuff of value.Therefore, desalination is of great significance to the processing of dyeing waste water.Membrane separation technique due to small investment, low energy consumption,
Rate of recovery height is at water treatment field very advantageous [J.Hazard.Mater, 2016,308:75-83].Traditional filtering film mainly divides
For two class of nanofiltration membrane and ultrafiltration membrane.Nanofiltration membrane is usually prepared with interfacial polymerization, and aperture is in nano-scale range, to big point
The retention of sub- dyestuff and small molecule inorganic salts is higher, while flux is smaller；Ultrafiltration membrane usually adds pore-foaming agent to prepare, flux compared with
Greatly, but to the retention of dyestuff poor [chemical equipment technology, 2002,23 (8): 14-17].Therefore, it is necessary to a kind of high-throughput, high
The filter membrane of macromolecular retention and the retention of low small molecule, is used for dye desalination.
Polyacrylonitrile is due to its good thermal stability, resistance to most of organic solvents, the characteristics such as resistance to bacterium and light radiation,
It is widely used in the fields such as clothes, industrial fabric, carbon fiber material, haemodialysis.Usually utilize organic solvent dissolution phase point
From polyacrylonitrile film is prepared, organic pollution being easily caused, while organic solvent solidification rate parameter is big, polymer solidification is violent,
Film forming has apparent finger-like pore supporting layer.And be studied many years ago with the PAN wet spinning of inorganic solvent zinc chloride, and
Realize industrialized production, but the more rare polyacrylonitrile filter membrane synthesized using zinc chloride as solvent.This team is with inorganic molten
Agent ZnCl2 aqueous solution is solvent, causes acrylonitrile polymerization with redox initiation system and obtains casting solution, using water as coagulating bath system
For homogeneous membrane [patent of invention ZL201610546688.2s, ZL of a series of sectional uniform densifications without finger-like pore
201610415071.7 ZL201610414768.2, ZL 201610414879.3, ZL 2016104149372].The series
Dyestuff of the polyacrylonitrile-radical filter membrane to molecular weight greater than 700 has good rejection effect, and exists to the rejection of inorganic salts
10% or less.
Membrane flux is an important process operating parameter of membrane separating process, in the case where keeping rejection constant, film
Flux is higher, and membrane separation efficiency is higher.Improving the main stream approach of membrane flux at present is to pass through organic solvent to the film of preparation
It is post-processed.But the use of organic solvent often reduces the mechanical performance of film, is unfavorable for the longtime running of film.
In the past few decades, monodisperse hollow microballoon is because having good pattern, uniform size, biggish specific surface
Long-pending and extensive potential using value causes the great interest of researcher.Such as: it can be with using the internal cavities of hollow microsphere
Loading and controlled release drug, gene, large biological molecule etc..Studying in inorganic hollow microspheres more mainly has SiO2、TiO2、
Fe3O4Deng.Wherein, hollow SiO2Microballoon is widely used in ultrasound because itself is nontoxic and has good chemical stability
Imaging, medicament slow release, catalysis and the fields such as heavy metal ion adsorbed.Hollow SiO2The wall of microballoon is relatively thin, hydrone and inorganic salts
Can pass through, and the biggish macromolecule of some macromoleculars especially viscosity be difficult to across.By hollow SiO2Microballoon is added to filtering
On the one hand on the other hand the antifouling property that film can be improved in film is expected to improve the flux of film.
For the flux for further increasing film, the present invention by the silane-modified hollow silica microsphere containing double bond functional group,
Double bond is introduced on hollow silica microsphere surface, and this microballoon is dispersed in solder(ing)acid, acrylonitrile is then added
Monomer, the second comonomer and initiator, cause Raolical polymerizable under stiring, obtain hollow silica microsphere grafting
Polyacrylonitrile-second comonomer copolymer casting solution.Preparing hollow microsphere as coagulating bath using water enhances high pass weight polyacrylonitrile
Filter membrane.The film retains height to dyestuff, and low to inorganic salts retention, has broad application prospects in dye desalination purification art.
Summary of the invention
In view of the deficiencies of the prior art, the technical issues of present invention intends to solve is that conventional film preparation process uses organic solvent
Cause environmental pollution, the problems such as polyacrylonitrile filter membrane hydrophily is poor, membrane flux is lower.
The present invention solution conventional film preparation process uses organic solvent and causes environmental pollution, polyacrylonitrile filter membrane parent
The technical solution of the problems such as aqueous poor, membrane flux is lower is to provide a kind of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane
Preparation method.
The present invention provides a kind of preparation methods of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane, it is characterized in that packet
Include following steps:
A) prepare mass percent concentration 0.01%-5% the silane-water solution containing double bond functional group, will be through overactivation at
The silicon dioxide hollow microsphere of reason is immersed in 0.5-24h in silane-water solution, obtains silica of the surface containing double bond functional group
Hollow microsphere；
B) solder(ing)acid of mass percent concentration 60% is prepared, weighing accounts for aqueous solution mass percent 0.01%-
Silicon dioxide hollow microsphere of the surface containing double bond functional group that 10% step a) is obtained, is scattered in solder(ing)acid
In, lead to nitrogen deoxygenation, is added under stiring and accounts for the acrylonitrile of aqueous solution mass percent 2%-50% and account for aqueous solution quality hundred
Divide the second comonomer than 1%-20%；
C) initiation for accounting for acrylonitrile and the second comonomer gross mass percentage 0.1%-10% is added dropwise under stiring
Agent, causes acrylonitrile and the second comonomer is graft-polymerized on silicon dioxide hollow microsphere of the surface containing double bond functional group, instead
It is 10-240min between seasonable, obtains casting solution；
D) aqueous solution that pH is 2-5 is prepared with dilute hydrochloric acid, as coagulating bath；
E) the obtained casting solution of step c) is poured on the glass plate of dry cleansing, is 10-1000 μ with both ends coiling diameter
The glass bar of m copper wire strikes off, and is immediately after put into the coagulating bath that step d) is obtained and impregnates 5- glass plate and the film scraped
Remaining zinc chloride and unreacted monomer is washed with deionized in 120min, and obtaining hollow microsphere enhances high-throughput polypropylene
Nitrile filter membrane；The hole wall of silicon dioxide hollow microsphere allows water and inorganic salts to pass through, since silicon dioxide hollow microsphere is not connect
Continuous, and be homogeneous using the polyacrylonitrile-radical filter membrane that solder(ing)acid is prepared as solvent, it is filtered without conventional polymer
The finger-like pore and compacted zone of film, therefore the introducing of silicon dioxide hollow microsphere also makes the logical of film without the cutoff performance of influence film
Amount improves 5%-100%.
The silane of double bond functional group of the present invention is γ-methacryloxypropyl trimethoxy silane, isobutyl
Allyloxy trimethoxy silane, vinyltriethoxysilane, any one or two kinds in vinyltrimethoxysilane
And the above mixture；Second comonomer is acrylamide, vinyl pyrrolidone, methyl acrylate, metering system
Any one in sour hydroxyl ethyl ester or two kinds and the above mixture；The initiator is potassium peroxydisulfate, sodium peroxydisulfate, persulfuric acid
Ammonium, sodium hydrogensulfite, ferrous sulfate, any one or two kinds and the above mixture in frerrous chloride.
Preparation method of the present invention is simple, and process is environmentally protective, and the film is high to figure dyestuff rejection, and retains to inorganic salts
Rate is lower than 5%, has broad application prospects in protein, dye desalination purification art.
Specific embodiment
Specific embodiments of the present invention are described below, but the present invention should not be limited by the examples.
Embodiment 1.
A) γ-methacryloxypropyl trimethoxy silane aqueous solution of mass percent concentration 0.01% is prepared,
It will be immersed in silane-water solution for 24 hours by the silicon dioxide hollow microsphere being activated, obtain surface containing double bond functional group's
Silicon dioxide hollow microsphere；
B) solder(ing)acid of mass percent concentration 60% is prepared, weighing accounts for aqueous solution mass percent 0.01%
Silicon dioxide hollow microsphere of the surface that step a) is obtained containing double bond functional group, is scattered in solder(ing)acid, and nitrogen is led to
Gas deoxygenation is added under stiring and accounts for the acrylonitrile of aqueous solution mass percent 2% and account for the propylene of aqueous solution mass percent 1%
Amide；
C) potassium peroxydisulfate-sulfurous for accounting for acrylonitrile and acrylamide gross mass percentage 0.1% is added dropwise under stiring
Sour sodium, causes acrylonitrile and acrylamide is graft-polymerized on silicon dioxide hollow microsphere of the surface containing double bond functional group, reacts
Time is 240min, obtains casting solution；
D) aqueous solution that pH is 2 is prepared with dilute hydrochloric acid, as coagulating bath；
E) the obtained casting solution of step c) is poured on the glass plate of dry cleansing, is 10 μm of copper wires with both ends coiling diameter
Glass bar strike off, glass plate and the film scraped are put into the coagulating bath that step d) is obtained impregnate 5min immediately after, spent
The zinc chloride of ionized water wash residual and unreacted monomer obtain hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane；Two
The hole wall of silica hollow microsphere allows water and inorganic salts to pass through, since silicon dioxide hollow microsphere is discontinuous, and with chlorine
Change zinc aqueous solution be solvent preparation polyacrylonitrile-radical filter membrane be homogeneous, without conventional polymer filter membrane finger-like pore and
Compacted zone, therefore the introducing of silicon dioxide hollow microsphere also makes the flux of film improve 5% without the cutoff performance of influence film.
Embodiment 2.
A) prepare mass percent concentration 5% isobutyl allyloxy trimethoxy silane aqueous solution, will be through overactivation at
The silicon dioxide hollow microsphere of reason is immersed in 12h in silane-water solution, obtains hollow silica of the surface containing double bond functional group
Microballoon；
B) solder(ing)acid for preparing mass percent concentration 60%, weighs the step for accounting for aqueous solution mass percent 10%
Rapid silicon dioxide hollow microsphere of surface a) obtained containing double bond functional group, is scattered in solder(ing)acid, and nitrogen is led to
Deoxygenation is added under stiring and accounts for the acrylonitrile of aqueous solution mass percent 50% and account for the ethylene of aqueous solution mass percent 20%
Base pyrrolidones；
C) persulfuric acid for accounting for acrylonitrile and vinyl pyrrolidone gross mass percentage 0.1% is added dropwise under stiring
Ammonium-sodium hydrogensulfite causes acrylonitrile and vinyl pyrrolidone in silicon dioxide hollow microsphere of the surface containing double bond functional group
Upper graft polymerization, reaction time 10min, obtains casting solution；
D) aqueous solution that pH is 5 is prepared with dilute hydrochloric acid, as coagulating bath；
E) the obtained casting solution of step c) is poured on the glass plate of dry cleansing, is 100 μm of copper with both ends coiling diameter
The glass bar of silk strikes off, and is immediately after put into the coagulating bath that step d) is obtained and impregnates 60min glass plate and the film scraped, and uses
The zinc chloride of deionized water wash residual and unreacted monomer obtain hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane；
The hole wall of silicon dioxide hollow microsphere allows water and inorganic salts to pass through, since silicon dioxide hollow microsphere is discontinuous, and with
Solder(ing)acid is that the polyacrylonitrile-radical filter membrane of solvent preparation is homogeneous, without the finger-like pore of conventional polymer filter membrane
And compacted zone, therefore the introducing of silicon dioxide hollow microsphere also improves the flux of film without the cutoff performance of influence film
100%.
Embodiment 3.
A) the vinyltriethoxysilane aqueous solution for preparing mass percent concentration 0.5%, will be by activation processing
Silicon dioxide hollow microsphere is immersed in 12h in silane-water solution, obtains silicon dioxide hollow microsphere of the surface containing double bond functional group；
B) solder(ing)acid for preparing mass percent concentration 60%, weighs the step for accounting for aqueous solution mass percent 5%
Rapid silicon dioxide hollow microsphere of surface a) obtained containing double bond functional group, is scattered in solder(ing)acid, and nitrogen is led to
Deoxygenation is added under stiring and accounts for the acrylonitrile of aqueous solution mass percent 10% and account for the propylene of aqueous solution mass percent 10%
Sour methyl esters；
C) sodium peroxydisulfate-sulphur for accounting for acrylonitrile and methyl acrylate gross mass percentage 0.5% is added dropwise under stiring
It is sour ferrous, cause acrylonitrile and methyl acrylate is graft-polymerized on silicon dioxide hollow microsphere of the surface containing double bond functional group,
Reaction time is 120min, obtains casting solution；
D) aqueous solution that pH is 3 is prepared with dilute hydrochloric acid, as coagulating bath；
E) the obtained casting solution of step c) is poured on the glass plate of dry cleansing, is 600 μm of copper with both ends coiling diameter
The glass bar of silk strikes off, and is immediately after put into the coagulating bath that step d) is obtained and impregnates 30min glass plate and the film scraped, and uses
The zinc chloride of deionized water wash residual and unreacted monomer obtain hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane；
The hole wall of silicon dioxide hollow microsphere allows water and inorganic salts to pass through, since silicon dioxide hollow microsphere is discontinuous, and with
Solder(ing)acid is that the polyacrylonitrile-radical filter membrane of solvent preparation is homogeneous, without the finger-like pore of conventional polymer filter membrane
And compacted zone, therefore the introducing of silicon dioxide hollow microsphere also makes the flux of film improve 60% without the cutoff performance of influence film.
Embodiment 4.
A) the vinyltrimethoxysilane aqueous solution for preparing mass percent concentration 1%, by two by activation processing
Silica hollow microsphere is immersed in 8h in silane-water solution, obtains silicon dioxide hollow microsphere of the surface containing double bond functional group；
B) solder(ing)acid for preparing mass percent concentration 60%, weighs the step for accounting for aqueous solution mass percent 1%
Rapid silicon dioxide hollow microsphere of surface a) obtained containing double bond functional group, is scattered in solder(ing)acid, and nitrogen is led to
Deoxygenation is added under stiring and accounts for the acrylonitrile of aqueous solution mass percent 15% and account for the methyl of aqueous solution mass percent 5%
Hydroxy-ethyl acrylate；
C) persulfuric acid for accounting for acrylonitrile and hydroxyethyl methacrylate gross mass percentage 2% is added dropwise under stiring
Ammonium-frerrous chloride causes acrylonitrile and hydroxyethyl methacrylate in silicon dioxide hollow microsphere of the surface containing double bond functional group
Upper graft polymerization, reaction time 60min, obtains casting solution；
D) aqueous solution that pH is 3 is prepared with dilute hydrochloric acid, as coagulating bath；
E) the obtained casting solution of step c) is poured on the glass plate of dry cleansing, is 500 μm of copper with both ends coiling diameter
The glass bar of silk strikes off, and is immediately after put into the coagulating bath that step d) is obtained and impregnates 60min glass plate and the film scraped, and uses
The zinc chloride of deionized water wash residual and unreacted monomer obtain hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane；
The hole wall of silicon dioxide hollow microsphere allows water and inorganic salts to pass through, since silicon dioxide hollow microsphere is discontinuous, and with
Solder(ing)acid is that the polyacrylonitrile-radical filter membrane of solvent preparation is homogeneous, without the finger-like pore of conventional polymer filter membrane
And compacted zone, therefore the introducing of silicon dioxide hollow microsphere also makes the flux of film improve 55% without the cutoff performance of influence film.
Claims (5)
1. a kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane, it is characterized in that the following steps are included:
A) silane-water solution containing double bond functional group for preparing mass percent concentration 0.01%-5%, will be by activation processing
Silicon dioxide hollow microsphere is immersed in 0.5-24h in silane-water solution, obtains hollow silica of the surface containing double bond functional group
Microballoon；
B) solder(ing)acid of mass percent concentration 60% is prepared, weighing accounts for aqueous solution mass percent 0.01%-10%
Obtained silicon dioxide hollow microsphere of the surface containing double bond functional group of step a), be scattered in solder(ing)acid, led to
Nitrogen deoxygenation is added under stiring and accounts for the acrylonitrile of aqueous solution mass percent 2%-50% and account for aqueous solution mass percent
The second comonomer of 1%-20%；
C) initiator for accounting for acrylonitrile and the second comonomer gross mass percentage 0.1%-10% is added dropwise under stiring, draws
Hair acrylonitrile and the second comonomer are graft-polymerized on silicon dioxide hollow microsphere of the surface containing double bond functional group, the reaction time
For 10-240min, casting solution is obtained；
D) aqueous solution that pH is 2-5 is prepared with dilute hydrochloric acid, as coagulating bath；
E) the obtained casting solution of step c) is poured on the glass plate of dry cleansing, is 10-1000 μm of copper with both ends coiling diameter
The glass bar of silk strikes off, and is immediately after put into the coagulating bath that step d) is obtained and impregnates 5- glass plate and the film scraped
Remaining zinc chloride and unreacted monomer is washed with deionized in 120min, and obtaining hollow microsphere enhances high-throughput polypropylene
Nitrile filter membrane；The hole wall of silicon dioxide hollow microsphere allows water and inorganic salts to pass through, since silicon dioxide hollow microsphere is not connect
Continuous, and be homogeneous using the polyacrylonitrile-radical filter membrane that solder(ing)acid is prepared as solvent, it is filtered without conventional polymer
The finger-like pore and compacted zone of film, therefore the introducing of silicon dioxide hollow microsphere also makes the logical of film without the cutoff performance of influence film
Amount improves 5%-100%.
2. a kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane as described in claim 1, it is characterized in that
The silane of the double bond functional group is γ-methacryloxypropyl trimethoxy silane, isobutyl allyloxy trimethoxy
Base silane, vinyltriethoxysilane, any one or two kinds and the above mixture in vinyltrimethoxysilane.
3. a kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane as described in claim 1, it is characterized in that
Second comonomer is acrylamide, vinyl pyrrolidone, methyl acrylate, appointing in hydroxyethyl methacrylate
Meaning one or two and the above mixture.
4. a kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane as described in claim 1, it is characterized in that
The initiator is potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, sodium hydrogensulfite, ferrous sulfate, any in frerrous chloride
The one or two kinds of and above mixture.
5. a kind of preparation method of hollow microsphere enhancing high pass weight polyacrylonitrile filter membrane as described in claim 1, it is characterized in that
Preparation method is simple, and process is environmentally protective, and the film is high to figure dyestuff rejection, and is lower than 5% to inorganic salt rejection rate, in egg
White matter, dye desalination purification art have broad application prospects.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113262651A (en) * | 2021-05-24 | 2021-08-17 | 武汉钜能科技有限责任公司 | Modified polyacrylonitrile ultrafiltration membrane applied to removing phosphate in water and preparation method thereof |
| CN114425241A (en) * | 2020-09-29 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method and application of copolymer film material containing silicon dioxide |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0574957A2 (en) * | 1989-04-14 | 1993-12-22 | Membrane Products Kiryat Weizmann Ltd. | Acrylonitrile- and polyvinylidene fluoride-derived membranes |
| CN101434708A (en) * | 2008-12-19 | 2009-05-20 | 成都中科来方能源科技有限公司 | Aqueous polymer modified micropore polyolefin barrier diaphragm, and preparation and use thereof |
| CN105854642A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Preparation method of hydrophilic polyacrylonitrile nanofiltration membrane with polyhydroxy |
| CN105854653A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing fibroin grafted polyacrylonitrile nanofiltration membrane |
| CN105854641A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing narrow-hole-diameter-distribution polyacrylonitrile nano-filtration membrane |
| CN106000134A (en) * | 2016-07-08 | 2016-10-12 | 天津工业大学 | Temperature-sensitive filtering membrane with small pore size distribution and preparation method thereof |
| CN107281940A (en) * | 2016-03-30 | 2017-10-24 | 天津工业大学 | A kind of polymer/polymer hollow microsphere hybridized film and application |
| CN107335344A (en) * | 2017-08-22 | 2017-11-10 | 天津工业大学 | Preparation method for the hollow-fibre membrane of dye desalination |
| CN108380055A (en) * | 2018-02-28 | 2018-08-10 | 天津大学 | The sodium alginate hybridized film of hollow ZIF-8 nano particles filling and preparation and application |
| CN108704495A (en) * | 2018-05-21 | 2018-10-26 | 天津工业大学 | A kind of preparation method of carboxylation titanium dioxide/calcium alginate compounded hydrogel filter membrane |
| CN108727628A (en) * | 2018-06-14 | 2018-11-02 | 常州大学 | A kind of nano silver tiny balloon/PVDF ultrafiltration membrane and preparation method thereof |
| CN108771983A (en) * | 2018-07-04 | 2018-11-09 | 青岛大学 | A kind of multilayer through-hole high penetration polymer micro-filter membrane and preparation method thereof |
-
2019
- 2019-04-04 CN CN201910269986.5A patent/CN110052177B/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0574957A2 (en) * | 1989-04-14 | 1993-12-22 | Membrane Products Kiryat Weizmann Ltd. | Acrylonitrile- and polyvinylidene fluoride-derived membranes |
| CN101434708A (en) * | 2008-12-19 | 2009-05-20 | 成都中科来方能源科技有限公司 | Aqueous polymer modified micropore polyolefin barrier diaphragm, and preparation and use thereof |
| CN107281940A (en) * | 2016-03-30 | 2017-10-24 | 天津工业大学 | A kind of polymer/polymer hollow microsphere hybridized film and application |
| CN105854642A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Preparation method of hydrophilic polyacrylonitrile nanofiltration membrane with polyhydroxy |
| CN105854653A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing fibroin grafted polyacrylonitrile nanofiltration membrane |
| CN105854641A (en) * | 2016-06-12 | 2016-08-17 | 天津工业大学 | Method for preparing narrow-hole-diameter-distribution polyacrylonitrile nano-filtration membrane |
| CN106000134A (en) * | 2016-07-08 | 2016-10-12 | 天津工业大学 | Temperature-sensitive filtering membrane with small pore size distribution and preparation method thereof |
| CN107335344A (en) * | 2017-08-22 | 2017-11-10 | 天津工业大学 | Preparation method for the hollow-fibre membrane of dye desalination |
| CN108380055A (en) * | 2018-02-28 | 2018-08-10 | 天津大学 | The sodium alginate hybridized film of hollow ZIF-8 nano particles filling and preparation and application |
| CN108704495A (en) * | 2018-05-21 | 2018-10-26 | 天津工业大学 | A kind of preparation method of carboxylation titanium dioxide/calcium alginate compounded hydrogel filter membrane |
| CN108727628A (en) * | 2018-06-14 | 2018-11-02 | 常州大学 | A kind of nano silver tiny balloon/PVDF ultrafiltration membrane and preparation method thereof |
| CN108771983A (en) * | 2018-07-04 | 2018-11-09 | 青岛大学 | A kind of multilayer through-hole high penetration polymer micro-filter membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZEHAI XU ET AL.: "Antimicrobial and pressure resistant polysulfone blended ultrafiltration membranes with core-shell ZnO microspheres", 《DESALINATION AND WATER TREATMENT》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114425241A (en) * | 2020-09-29 | 2022-05-03 | 中国石油化工股份有限公司 | Preparation method and application of copolymer film material containing silicon dioxide |
| CN114425241B (en) * | 2020-09-29 | 2023-07-21 | 中国石油化工股份有限公司 | Preparation method and application of copolymer film material containing silicon dioxide |
| CN113262651A (en) * | 2021-05-24 | 2021-08-17 | 武汉钜能科技有限责任公司 | Modified polyacrylonitrile ultrafiltration membrane applied to removing phosphate in water and preparation method thereof |
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