CN110052174A - A kind of preparation method of the polyacrylonitrile-radical filter membrane of high throughput bubbles - Google Patents
A kind of preparation method of the polyacrylonitrile-radical filter membrane of high throughput bubbles Download PDFInfo
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- CN110052174A CN110052174A CN201910269763.9A CN201910269763A CN110052174A CN 110052174 A CN110052174 A CN 110052174A CN 201910269763 A CN201910269763 A CN 201910269763A CN 110052174 A CN110052174 A CN 110052174A
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- bubbles
- polyacrylonitrile
- filter membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000005266 casting Methods 0.000 claims abstract description 23
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002253 acid Substances 0.000 claims abstract description 21
- 229910000679 solder Inorganic materials 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 230000001112 coagulating effect Effects 0.000 claims abstract description 15
- 229920002521 macromolecule Polymers 0.000 claims abstract description 15
- 239000000975 dye Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 238000010612 desalination reaction Methods 0.000 claims abstract description 8
- 238000009826 distribution Methods 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 102000004169 proteins and genes Human genes 0.000 claims abstract description 4
- 108090000623 proteins and genes Proteins 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 239000011521 glass Substances 0.000 claims description 18
- 238000010907 mechanical stirring Methods 0.000 claims description 18
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 235000005074 zinc chloride Nutrition 0.000 claims description 9
- 239000011592 zinc chloride Substances 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000011148 porous material Substances 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000033228 biological regulation Effects 0.000 claims description 4
- 238000006392 deoxygenation reaction Methods 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Chemical compound [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 3
- 239000011790 ferrous sulphate Substances 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 claims description 3
- 235000010262 sodium metabisulphite Nutrition 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 229940079827 sodium hydrogen sulfite Drugs 0.000 claims description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- 230000000977 initiatory effect Effects 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims 1
- 235000019394 potassium persulphate Nutrition 0.000 claims 1
- 230000001681 protective effect Effects 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000013019 agitation Methods 0.000 abstract description 2
- 229920001577 copolymer Polymers 0.000 abstract description 2
- 239000006260 foam Substances 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 230000004907 flux Effects 0.000 description 13
- 229920002239 polyacrylonitrile Polymers 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000004043 dyeing Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- SATQNYRZLIROHO-UHFFFAOYSA-N [NH4+].[Na].OS([O-])=O Chemical compound [NH4+].[Na].OS([O-])=O SATQNYRZLIROHO-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000001631 haemodialysis Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229910001867 inorganic solvent Inorganic materials 0.000 description 1
- 239000003049 inorganic solvent Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000032696 parturition Effects 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical group 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012966 redox initiator Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000002166 wet spinning Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The present invention provides a kind of preparation methods of the polyacrylonitrile-radical filter membrane of high-throughput bubbles, and the film is applied to dye desalination.Solder(ing)acid is prepared first, and dissolution hydrophilic macromolecule introduces hydrophilic functional groups.Then acrylonitrile monemer, the second comonomer and initiator is added, causes the homogeneous graft reaction of free radical under stiring, obtains polyacrylonitrile-second comonomer copolymer casting solution of hydrophilic macromolecule grafting.The viscosity of casting solution is adjusted by the way that hydrophilic macromolecule and the second comonomer is added, bubble is introduced under agitation, content, size and the distribution of bubble is controlled by control mixing speed, mixing time and vacuum foam time.Bubbles high pass weight polyacrylonitrile-base filter membrane is prepared by coagulating bath of water.The film is high to protein and figure dyestuff rejection, and has broad application prospects almost without retention in protein, dye desalination purification art to inorganic salts.
Description
Technical field
The present invention relates to a kind of preparation method of the polyacrylonitrile-radical filter membrane of high-throughput bubbles, belong to functional material and
UF membrane field.
The present invention relates to the technical fields such as polyacrylonitrile, filter membrane, polymerization reaction.More particularly to a kind of high-throughput bubbles
Polyacrylonitrile-radical filter membrane preparation method, and its application in dye wastewater treatment and dye desalination.
Background technique
Dyeing waste water is due to one of the main reason for its toxicity, high salinity and coloration become water pollution.Dyeing waste water it is straight
Run in and put and can have a negative impact to water ecosystem, and wastes a large amount of valuable dyestuffs.Therefore, desalination is to dyeing waste water
Processing be of great significance.Membrane separation technique due to small investment, low energy consumption, the rate of recovery is high, to environment without negative effect, in water
Process field very advantageous.Traditional filtering film is broadly divided into nanofiltration membrane, two class of ultrafiltration membrane.Nanofiltration membrane usually uses interfacial polymerization legal system
Standby, aperture is in nano-scale range, higher to the retention of macromolecular dyestuff and small molecule inorganic salts, at the same flux compared with
It is small；Ultrafiltration membrane usually adds pore-foaming agent to prepare, and flux is larger, but poor to the retention of dyestuff.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 clothes, industrial fabric, carbon fiber material, the fields such as haemodialysis.Usual polyacrylonitrile film utilizes organic molten
Agent dissolution mutually separation preparation, easily causes organic pollution, while organic solvent solidification rate parameter is big, and polymer solidification is violent,
Film forming has apparent finger-like pore supporting layer, therefore the elimination of bubble is particularly important, and that otherwise easily causes film rushes down leakage.With inorganic molten
The PAN wet spinning of agent zinc chloride has been studied many years ago, and realizes industrialized production, but more rare with zinc chloride
For the polyacrylonitrile filter membrane of solvent synthesis.This team is solvent with inorganic solvent ZnCl2 aqueous solution, with Redox Initiator body
System causes acrylonitrile polymerization and obtains casting solution, is prepared for a series of homogeneous of the sectional uniform densification without finger-like pore by coagulating bath of water
Film [patent of invention ZL201610546688.2, ZL 201610415071.7, ZL 201610414768.2, ZL
201610414879.3 ZL 2016104149372].The polyacrylonitrile-radical filter membrane of the series is greater than 700 dye to molecular weight
Material has good rejection effect, and to the rejection of inorganic salts below 10%.
Membrane flux is an important process operating parameter of membrane separating process, refers to and passes through per membrane area in the unit time
On fluid volume.In the case where keeping rejection constant, membrane flux is higher, and membrane separation efficiency is higher.It mentions at present
The main stream approach of high membrane flux is to be post-processed to the film of preparation by organic solvent.But the use of organic solvent is often
The mechanical performance for reducing film, is unfavorable for the longtime running of film.Fouling membrane is also a key factor for influencing UF membrane, conventional film
Material is due to its hydrophobicity, it is easy to cause fouling membrane, reduce flux, energy consumption increases.Reduce fouling membrane strategy be mainly
Improve the hydrophily of film, such as blending and modifying, surface coating and hydrophilic macromolecule graft modification.The technique of blending and modifying compared with
Difficult to control, the water wetted material of film surface coating is easy to fall off, and the hydrophilic high mol of surface grafting is difficult to reach and uniformly sprawl.And it will be high
Molecule obtains modified polymer film with knifing after hydrophilic polymer graft reaction and not only reaches hydrophilic modifying, but also surface is avoided to connect
The problem that branch unevenly waits.
The present invention provides a kind of preparation methods of the polyacrylonitrile-radical filter membrane of high-throughput bubbles, and by the film application
In dye desalination.Solder(ing)acid is prepared first, and dissolution hydrophilic macromolecule introduces hydrophilic functional groups.Then acrylonitrile is added
Monomer, the second comonomer and initiator cause the homogeneous graft reaction of free radical under stiring, obtain hydrophilic macromolecule grafting
Polyacrylonitrile-second comonomer copolymer casting solution.Casting solution is adjusted by the way that hydrophilic macromolecule and the second comonomer is added
Viscosity, introduce bubble under agitation, pass through control mixing speed, mixing time and vacuum foam time control bubble
Content, size and distribution.The polyacrylonitrile-radical filter membrane of high-throughput bubbles is prepared using water as coagulating bath.High-throughput bubbles
Polyacrylonitrile-radical filter membrane broken " Trade-off " rule, for improve filtering membrane efficiency research provide new thinking.
The film is high to figure dyestuff rejection, and has in protein, dye desalination purification art wide to inorganic salts almost without retention
Application prospect.
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, flux is lower.
The present invention solves the conventional film preparation process and causes environmental pollution, polyacrylonitrile filter membrane parent using organic solvent
The technical solution of the problems such as aqueous poor, flux is lower is to provide a kind of preparation of the polyacrylonitrile-radical filter membrane of high-throughput bubbles
Method.
The present invention provides a kind of preparation methods of the polyacrylonitrile-radical filter membrane of high-throughput bubbles, it is characterized in that including
Following steps:
A) solder(ing)acid of mass percent concentration 60% is prepared, weighing accounts for aqueous solution mass percent 0.5%-
20% hydrophilic macromolecule is dissolved in solder(ing)acid, and the solder(ing)acid for dissolving hydrophilic macromolecule is poured into three mouthfuls
In flask, lead to nitrogen deoxygenation, is added under mechanical stirring and accounts for the acrylonitrile of aqueous solution mass percent 2%-50% and account for water-soluble
The second comonomer of liquid mass percent 1%-20%；
B) it is added dropwise under mechanical stirring and accounts for acrylonitrile and the second comonomer gross mass percentage 0.1%-10%
Initiator, causes acrylonitrile and the second comonomer is graft-polymerized on hydrophilic macromolecule, reaction time 20-240min；
0.1-5h is stirred with the stirring rate that 20-1200 per minute turns under mechanical stirring after reaction, obtains bubble volume percentage
Than for 0.1%-60%, the casting solution for the bubbles that Air Bubble Size is 1-200 μm；It is produced by control mixing speed and mixing time
The bubble for giving birth to different size, distribution and percent by volume, the casting solution of bubbles is placed into vacuum oven and is vacuumized, and is led to
Overregulate the percent by volume of vacuum degree and pumpdown time regulation Air Bubble Size and bubble；
C) aqueous solution that pH is 2-5 is prepared with dilute hydrochloric acid, as coagulating bath；
D) casting solution of the obtained bubbles of step b) is poured on the glass plate of dry cleansing, is with both ends coiling diameter
The glass bar of 10-1000 μm of copper wire strikes off, and glass plate and the film scraped are put into the coagulating bath that step c) is obtained immediately after
5-120min is impregnated, remaining zinc chloride and unreacted monomer is washed with deionized, obtains the polyacrylonitrile-radical of bubbles
Filter membrane；Since the bubble in filter membrane is not connected to, and the polyacrylonitrile-radical filter membrane of this method preparation is homogeneous, is not passed
The finger-like pore and compacted zone of system macromolecular filtering film, therefore the introducing of bubble also makes film not only without the cutoff performance of influence film
Flux improve 5%-90%.
Hydrophilic macromolecule of the present invention is polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol
In any one or two kinds and the above mixture；Second comonomer is acrylamide, vinyl pyrrolidone, third
Any one in e pioic acid methyl ester, hydroxyethyl methacrylate or two kinds and the above mixture；The initiator is persulfuric acid
Potassium, sodium peroxydisulfate, ammonium persulfate, sodium pyrosulfite, sodium hydrogensulfite, ferrous sulfate, in frerrous chloride any one or two
Kind and the above mixture.
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) solder(ing)acid of mass percent concentration 60% is prepared, weighing accounts for aqueous solution mass percent 0.5%
Polyacrylamide is dissolved in solder(ing)acid, and the solder(ing)acid for dissolving polyacrylamide is poured into three-necked flask, leads to
Nitrogen deoxygenation is added under mechanical stirring and accounts for the acrylonitrile of aqueous solution mass percent 2% and account for aqueous solution mass percent 1%
Acrylamide；
B) potassium peroxydisulfate-for accounting for acrylonitrile and acrylamide gross mass percentage 0.1% is added dropwise under mechanical stirring
Sodium pyrosulfite, causes acrylonitrile and acrylamide is graft-polymerized on polyacrylamide, reaction time 20min；Reaction knot
0.1h is stirred with 20 turns of stirring rate per minute under mechanical stirring after beam, obtaining bubble volume percentage is 0.1%, bubble
The casting solution for the bubbles that size is 1 μm；Different size, distribution and volume hundred are generated by control mixing speed and mixing time
The bubble for dividing ratio, the casting solution of bubbles is placed into vacuum oven and is vacuumized, when by adjusting vacuum degree and vacuumize
Between regulate and control Air Bubble Size and bubble percent by volume；
C) aqueous solution that pH is 2 is prepared with dilute hydrochloric acid, as coagulating bath；
D) casting solution of the obtained bubbles of step b) is poured on the glass plate of dry cleansing, is with both ends coiling diameter
The glass bar of 10 μm of copper wires strikes off, and glass plate and the film scraped are put into the coagulating bath that step c) is obtained and are impregnated immediately after
Remaining zinc chloride and unreacted monomer is washed with deionized in 5min, obtains the polyacrylonitrile-radical filter membrane of bubbles；By
Bubble in filter membrane is not connected to, and the polyacrylonitrile-radical filter membrane of this method preparation is homogeneous, without conventional polymer
The finger-like pore and compacted zone of filter membrane, therefore the introducing of bubble also mentions the flux of film not only without the cutoff performance of influence film
It is high by 5%.
Embodiment 2.
A) solder(ing)acid for preparing mass percent concentration 60% weighs and accounts for the poly- of aqueous solution mass percent 1%
Vinyl alcohol is dissolved in solder(ing)acid, and the solder(ing)acid of polyethylene dissolving alcohol is poured into three-necked flask, leads to nitrogen row
Oxygen is added under mechanical stirring and accounts for the acrylonitrile of aqueous solution mass percent 50% and account for the second of aqueous solution mass percent 20%
Vinyl pyrrolidone；
B) over cure for accounting for acrylonitrile and vinyl pyrrolidone gross mass percentage 10% is added dropwise under mechanical stirring
Sour ammonium-sodium hydrogensulfite causes acrylonitrile and vinyl pyrrolidone and is graft-polymerized on polyvinyl alcohol, and the reaction time is
240min；5h is stirred with 20 turns of stirring rate per minute under mechanical stirring after reaction, obtains bubble volume percentage
It is 60%, the casting solution for the bubbles that Air Bubble Size is 200 μm；It is generated Bu Tong greatly by control mixing speed and mixing time
Small, distribution and percent by volume bubble, the casting solution of bubbles is placed into vacuum oven and is vacuumized, true by adjusting
The percent by volume of reciprocal of duty cycle and pumpdown time regulation Air Bubble Size and bubble；
C) aqueous solution that pH is 5 is prepared with dilute hydrochloric acid, as coagulating bath；
D) casting solution of the obtained bubbles of step b) is poured on the glass plate of dry cleansing, is with both ends coiling diameter
The glass bar of 1000 μm of copper wires strikes off, and glass plate and the film scraped are put into the coagulating bath that step c) is obtained and are impregnated immediately after
Remaining zinc chloride and unreacted monomer is washed with deionized in 120min, obtains the polyacrylonitrile-radical filter membrane of bubbles；
Since the bubble in filter membrane is not connected to, and the polyacrylonitrile-radical filter membrane of this method preparation is homogeneous, without tradition high score
The finger-like pore and compacted zone of sub- filter membrane, therefore the introducing of bubble also makes the flux of film not only without the cutoff performance of influence film
Improve 90%.
Embodiment 3.
A) solder(ing)acid for preparing mass percent concentration 60% weighs and accounts for the poly- of aqueous solution mass percent 20%
Vinylpyrrolidone is dissolved in solder(ing)acid, and the solder(ing)acid of polyethylene dissolving pyrrolidones is poured into three-necked flask
In, lead to nitrogen deoxygenation, is added under mechanical stirring and accounts for the acrylonitrile of aqueous solution mass percent 20% and account for aqueous solution quality hundred
Divide the methyl acrylate than 20%；
B) sodium peroxydisulfate-for accounting for acrylonitrile and methyl acrylate gross mass percentage 5% is added dropwise under mechanical stirring
Ferrous sulfate, causes acrylonitrile and methyl acrylate is graft-polymerized on polyvinylpyrrolidone, reaction time 100min；Instead
2h is stirred with 200 turns of stirring rate per minute under mechanical stirring after answering, obtaining bubble volume percentage is 40%, gas
Steep the casting solution for the bubbles that size is 50 μm；Different size, distribution and body are generated by control mixing speed and mixing time
The bubble of product percentage, the casting solution of bubbles is placed into vacuum oven and is vacuumized, by adjusting vacuum degree and taking out true
The percent by volume of empty time-controllable Air Bubble Size and bubble；
C) aqueous solution that pH is 4 is prepared with dilute hydrochloric acid, as coagulating bath；
D) casting solution of the obtained bubbles of step b) is poured on the glass plate of dry cleansing, is with both ends coiling diameter
The glass bar of 800 μm of copper wires strikes off, and glass plate and the film scraped are put into the coagulating bath that step c) is obtained and are impregnated immediately after
Remaining zinc chloride and unreacted monomer is washed with deionized in 60min, obtains the polyacrylonitrile-radical filter membrane of bubbles；
Since the bubble in filter membrane is not connected to, and the polyacrylonitrile-radical filter membrane of this method preparation is homogeneous, without tradition high score
The finger-like pore and compacted zone of sub- filter membrane, therefore the introducing of bubble also makes the flux of film not only without the cutoff performance of influence film
Improve 60%.
Embodiment 4.
A) solder(ing)acid for preparing mass percent concentration 60% weighs and accounts for the poly- of aqueous solution mass percent 10%
Ethylene glycol is dissolved in solder(ing)acid, and the solder(ing)acid for dissolving polyethylene glycol is poured into three-necked flask, leads to nitrogen row
Oxygen is added under mechanical stirring and accounts for the acrylonitrile of aqueous solution mass percent 10% and account for the first of aqueous solution mass percent 10%
Base hydroxy-ethyl acrylate；
B) over cure for accounting for acrylonitrile and hydroxyethyl methacrylate gross mass percentage 2% is added dropwise under mechanical stirring
Sour ammonium-frerrous chloride causes acrylonitrile and hydroxyethyl methacrylate and is graft-polymerized on polyethylene glycol, and the reaction time is
120min；2h is stirred with 300 turns of stirring rate per minute under mechanical stirring after reaction, obtains bubble volume percentage
It is 50%, the casting solution for the bubbles that Air Bubble Size is 40 μm；By control mixing speed and mixing time generate different size,
The bubble of distribution and percent by volume, the casting solution of bubbles is placed into vacuum oven and is vacuumized, by adjusting vacuum
The percent by volume of degree and pumpdown time regulation Air Bubble Size and bubble；
C) aqueous solution that pH is 3 is prepared with dilute hydrochloric acid, as coagulating bath；
D) casting solution of the obtained bubbles of step b) is poured on the glass plate of dry cleansing, is with both ends coiling diameter
The glass bar of 500 μm of copper wires strikes off, and glass plate and the film scraped are put into the coagulating bath that step c) is obtained and are impregnated immediately after
Remaining zinc chloride and unreacted monomer is washed with deionized in 30min, obtains the polyacrylonitrile-radical filter membrane of bubbles；
Since the bubble in filter membrane is not connected to, and the polyacrylonitrile-radical filter membrane of this method preparation is homogeneous, without tradition high score
The finger-like pore and compacted zone of sub- filter membrane, therefore the introducing of bubble also makes the flux of film not only without the cutoff performance of influence film
Improve 40%.
Claims (5)
1. a kind of preparation method of the polyacrylonitrile-radical filter membrane of high throughput bubbles, it is characterized in that the following steps are included:
A) solder(ing)acid of mass percent concentration 60% is prepared, weighing accounts for aqueous solution mass percent 0.5%-20%'s
Hydrophilic macromolecule is dissolved in solder(ing)acid, and the solder(ing)acid for dissolving hydrophilic macromolecule is poured into three-necked flask
In, lead to nitrogen deoxygenation, is added under mechanical stirring and accounts for the acrylonitrile of aqueous solution mass percent 2%-50% and account for aqueous solution matter
Measure the second comonomer of percentage 1%-20%；
B) initiation for accounting for acrylonitrile and the second comonomer gross mass percentage 0.1%-10% is added dropwise under mechanical stirring
Agent, causes acrylonitrile and the second comonomer is graft-polymerized on hydrophilic macromolecule, reaction time 20-240min；Reaction
After under mechanical stirring with 20-1200 per minute turn stirring rate stir 0.1-5h, obtaining bubble volume percentage is
0.1%-60%, the casting solution for the bubbles that Air Bubble Size is 1-200 μm；It is generated not by control mixing speed and mixing time
Same size, distribution and percent by volume bubble, the casting solution of bubbles is placed into vacuum oven and is vacuumized, tune is passed through
Save the percent by volume of vacuum degree and pumpdown time regulation Air Bubble Size and bubble；
C) aqueous solution that pH is 2-5 is prepared with dilute hydrochloric acid, as coagulating bath；
D) casting solution of the obtained bubbles of step b) is poured on the glass plate of dry cleansing, is 10- with both ends coiling diameter
The glass bar of 1000 μm of copper wires strikes off, and glass plate and the film scraped are put into the coagulating bath that step c) is obtained and are impregnated immediately after
Remaining zinc chloride and unreacted monomer is washed with deionized in 5-120min, obtains the polyacrylonitrile-radical filtering of bubbles
Film；Since the bubble in filter membrane is not connected to, and the polyacrylonitrile-radical filter membrane of this method preparation is homogeneous, high without tradition
The finger-like pore and compacted zone of molecular filtration membrane, therefore the introducing of bubble also makes the logical of film not only without the cutoff performance of influence film
Amount improves 5%-90%.
2. a kind of preparation method of the polyacrylonitrile-radical filter membrane of high-throughput bubbles as described in claim 1, it is characterized in that institute
The hydrophilic macromolecule stated be polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, in polyethylene glycol any one or two
Kind and the above mixture.
3. a kind of preparation method of the polyacrylonitrile-radical filter membrane of high-throughput bubbles as described in claim 1, it is characterized in that institute
The second comonomer stated is acrylamide, vinyl pyrrolidone, methyl acrylate, any in hydroxyethyl methacrylate
The one or two kinds of and above mixture.
4. a kind of preparation method of the polyacrylonitrile-radical filter membrane of high-throughput bubbles as described in claim 1, it is characterized in that institute
The initiator stated is potassium peroxydisulfate, sodium peroxydisulfate, ammonium persulfate, sodium pyrosulfite, sodium hydrogensulfite, ferrous sulfate, protochloride
Any one in iron or two kinds and the above mixture.
5. a kind of preparation method of the polyacrylonitrile-radical filter membrane of high-throughput bubbles as described in claim 1, it is characterized in that system
Preparation Method is simple, and process is environmentally protective, has good popularization and application foreground in dyestuff and protein desalination field.
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