CN106422808A - Super-hydrophilic polyacrylonitrile hollow fiber ultra-filtration membrane and preparation method thereof - Google Patents
Super-hydrophilic polyacrylonitrile hollow fiber ultra-filtration membrane and preparation method thereof Download PDFInfo
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- CN106422808A CN106422808A CN201510489114.1A CN201510489114A CN106422808A CN 106422808 A CN106422808 A CN 106422808A CN 201510489114 A CN201510489114 A CN 201510489114A CN 106422808 A CN106422808 A CN 106422808A
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- polypropylene
- hollow fiber
- ultrafiltration membrane
- fine
- polyvinyl alcohol
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- 239000012528 membrane Substances 0.000 title claims abstract description 84
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 68
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 229920002239 polyacrylonitrile Polymers 0.000 title abstract 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 59
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 59
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004743 Polypropylene Substances 0.000 claims description 72
- -1 polypropylene Polymers 0.000 claims description 67
- 229920001155 polypropylene Polymers 0.000 claims description 66
- 238000009987 spinning Methods 0.000 claims description 34
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 21
- 238000004804 winding Methods 0.000 claims description 20
- 239000003361 porogen Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 9
- 235000012489 doughnuts Nutrition 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 7
- 230000009471 action Effects 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 230000001112 coagulating effect Effects 0.000 claims description 7
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 7
- 239000001117 sulphuric acid Substances 0.000 claims description 7
- 235000011149 sulphuric acid Nutrition 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229960003511 macrogol Drugs 0.000 claims description 6
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 claims description 6
- 235000015165 citric acid Nutrition 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000008118 PEG 6000 Substances 0.000 claims description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 2
- 229920003082 Povidone K 90 Polymers 0.000 claims description 2
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 2
- 229920001223 polyethylene glycol Polymers 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000835 fiber Substances 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- 150000003462 sulfoxides Chemical class 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004132 cross linking Methods 0.000 abstract 1
- 230000032798 delamination Effects 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 230000008569 process Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 229920003081 Povidone K 30 Polymers 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229940057847 polyethylene glycol 600 Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
The present invention relates to the technical field of hydrophilic hollow fiber ultra-filtration membranes, more particularly to a super-hydrophilic polyacrylonitrile hollow fiber ultra-filtration membrane and a preparation method thereof. The preparation method comprises: blending polyacrylonitrile and polyvinyl alcohol to prepare a hollow fiber ultra-filtration membrane, wherein the use amount of the polyvinyl alcohol is controlled at 2-20% of the total mass of the mixture of polyacrylonitrile and polyvinyl alcohol; grafting a cross-linking agent onto the surface of the prepared hollow fiber ultra-filtration membrane through a cross-linking effect under the effect of concentrated sulfuric acid with a mass percentage of 1%; and repeatedly washing at a temperature of 60 DEG C with reverse osmosis water so as to obtain the super-hydrophilic polyacrylonitrile hollow fiber ultra-filtration membrane, wherein the membrane water contact angle is as low as less than 3.2 DEG, and the hydrophilicity and the anti-pollution property are excellent; and the operation of the production method is simple, the preparation parameters are easy to control, the membrane stability is excellent, and delamination is not easily generated.
Description
Technical field
The present invention relates to hydrophilic hollow fiber ultrafiltration membrane technical field, especially a kind of super hydrophilic
Property fine hollow fiber ultrafiltration membrane of polypropylene and preparation method thereof.
Background technology
Membrane technology, the high efficiency being had due to it, energy-conserving and environment-protective, productivity ratio are higher, Neng Gouli
With low-grade characteristic so that it more meets the demand of modern industry filtration art, simultaneously
Also overcome the defect of traditional low separation efficiency, high energy consumption, separation process, and then be employed
In the every field of life, such as sewage disposal, desalinization, health care, energy-conserving and environment-protective etc..
Hollow fiber ultrafiltration membrane be develop earliest and occur in fractionated polymer in commercial Application from
One of film, it is by the substantial amounts of separation being applied to the every profession and trades such as electronics, chemical industry, medicine, food
With purification art；But, application film during, due to separate, purge process so that
The pollution of film becomes the more prominent technical problem of film application, and then has substantial amounts of research
Person is directed to hydrophilic of the cleaning of film, film purification and film etc. and is studied, and it is believed that
Control for the pollution condition on film surface and reduction, can be by increasing the hydrophilic of film surface
Property improving the contamination resistance on film surface, and then in the prior art, occur in that using parent
The preferable material of aqueouss is directly prepared ultrafilter membrane and ultrafiltration membrane surface is carried out hydrophilically modified
Technical literature.
Mainly include physical blending, surface-coated currently for the hydrophilically modified method of ultrafilter membrane
And surface grafting；Wherein, physical blending is that hydroaropic substance is blended with polymer, and is changing
Property during add porogen improving the flux of diaphragm；Surface-coated is by the surface of hydrophobic membrane
Apply last layer hydrophilic polymer, then carry out heat treatment or chemical treatment so that coating is fixed,
This coat that easily causes is unstable, is easy in high temperature environments come off；Surface grafting be
Under conditions of certain, introduce hydrophilic group so that it changes the table of hydrophobic membrane on hydrophobic membrane surface
Surface properties, mainly surface chemical reaction make to be formed chemistry between modified monomer and ultrafilter membrane
Key；But, the hollow fiber ultrafiltration membrane prepared in the prior art, it is used for because it lacks one kind
The active group reacting further, in turn resulting in it, to carry out the difficulty of chemical reaction larger.
Content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of super close
Fine hollow fiber ultrafiltration membrane of aqueous polyacrylamide and preparation method thereof.
It is achieved particular by technical scheme below：
A kind of fine hollow fiber ultrafiltration membrane preparation method of Superhydrophilic polypropylene, polypropylene is warm and fine
Polyvinyl alcohol blending prepares hollow fiber ultrafiltration membrane, and wherein polyvinyl alcohol consumption is that polypropylene is warm and fine
The 2-20% of the gross mass of polyvinyl alcohol consumption；Again by the hollow fiber ultrafiltration membrane preparing in matter
In the presence of amount percentage ratio accounts for 1% concentrated sulphuric acid, by crosslinked action by cross-linking agent A and cross-linking agent
B is grafted to the surface of ultrafilter membrane, and the consumption of wherein cross-linking agent A and crosslinking agent B is with percent mass
Respectively account for 0.05-2% than meter.
Described prepares hollow fiber ultrafiltration membrane by warm and fine for polypropylene polyvinyl alcohol blending, is will be poly-
Propylene is fine, polyvinyl alcohol and porogen are poured into equipped with the reactor of organic solvent, mechanical agitation
Mix homogeneously, standing vacuum defoamation obtains clear transparent solutions, then controls temperature at 25 DEG C, opens
The outlet valve of reactor, and into reactor in be passed through nitrogen so that the pressure in reactor is
0.2MPa, then opens spinning pump, the rotating speed controlling spinning pump in 30r/min, and by spinning
The doughnut that the spinning head of pump is extruded through 20 DEG C coagulating bath process after, by its wound on
On wind-up roll, the rotating speed of wind-up roll winding controls in 25r/min, after spinning terminates, from winding
The film of winding is taken off on roller, is placed on immersion 45-50h in reverse osmosis water, then is put
In mass percent be 50% glycerine water solution in soak 45-50h, then be placed on room temperature do
Dry the fine hollow fiber ultrafiltration membrane of polypropylene.
Described polypropylene is fine, its with polyvinyl alcohol after the mass percent that accounts for of gross mass
For 10-25%, the wherein mass percent of polyvinyl alcohol is to account for the warm and fine polyvinyl alcohol of polypropylene
The 2-20% of total amount afterwards；Described organic solvent, its mass percent is 60-85%；Described
Porogen, its mass percent be 2-15%.
Described organic solvent is N-Methyl pyrrolidone (NMP), N, N- dimethyl formyl
Amine (DMF), N,N-dimethylacetamide (DMAC), dimethyl sulfoxide (DMSO)
Any one.
Described porogen is PEG400 (PEG400), PEG600 (Polyethylene Glycol
600), PEG1000 (Macrogol 1000), PEG2000 (Macrogol 2000), PEG6000
(polyethylene glycol 6000), PEG10000 (PEG20000), PVPK15(polyethylene pyrrole
Pyrrolidone K15), PVPK30(PVP K30), PVPK40(polyvinyl pyrrole
Alkanone k40), PVPK60(Polyvinylpyrrolidone k60), PVPK80(Polyvinylpyrrolidone
k80)、PVPk90Any one of (PVP K90) or lithium chloride (LiCl).
Described cross-linking agent A is citric acid, oxalic acid, malic acid, any one in tartaric acid.
Described crosslinking agent B is glutaraldehyde.
Described vacuum defoamation, its vacuum is -0.05～-0.1MPa.
Described preparation method, after cross-linking agent A and crosslinking agent B are grafted to ultrafiltration membrane surface,
Also include the step being adopted reverse osmosis water cleaning.
Described reverse osmosis water, its temperature is 50-70 DEG C, and more excellent is 60 DEG C.
Compared with prior art, the technique effect of the present invention is embodied in：
By the method using blending, the macromolecule with active group is added to repair in casting solution
Jewelry, and its addition is controlled so that adding generation phase interaction between each material composition
With, and then make the hydrophilicity preparing the fine hollow fiber ultrafiltration membrane of Superhydrophilic polypropylene steady
Fixed, clear water layer not easily runs off, and the pure water flux after repeatedly cleaning can reach and do not carry out cross-linked graft
More than 90% processing, and, the fine hollow fiber ultrafiltration membrane of this hydrophilic polypropylene carried out with water
During contact experiment test, its contact angle with water is less than 3.2 °, has superior hydrophilic
Performance and contamination resistance.
Brief description
Fig. 1 is the sectional view of the fine hollow fiber ultrafiltration membrane of Superhydrophilic polypropylene of the present invention.
Fig. 2 is the AFM figure of the fine hollow fiber ultrafiltration membrane of Superhydrophilic polypropylene of the present invention.
Fig. 3 is the film water contact angle of the fine hollow fiber ultrafiltration membrane of Superhydrophilic polypropylene of the present invention
Test result schematic diagram.
Specific embodiment
Technical scheme is further limited with reference to specific embodiment
Fixed, but claimed scope is not only limited to description.
Embodiment 1
A kind of fine hollow fiber ultrafiltration membrane preparation method of Superhydrophilic polypropylene, polypropylene is warm and fine
Polyvinyl alcohol blending prepares hollow fiber ultrafiltration membrane, and wherein polyvinyl alcohol consumption is that polypropylene is warm and fine
The 13.8% of the gross mass of polyvinyl alcohol consumption；Again by the hollow fiber ultrafiltration membrane preparing in matter
In the presence of amount percentage ratio accounts for 1% concentrated sulphuric acid, by crosslinked action by cross-linking agent A and cross-linking agent
B is grafted to the surface of ultrafilter membrane, and the consumption of wherein cross-linking agent A and crosslinking agent B is with percent mass
Respectively account for 0.05% than meter.
Described prepares hollow fiber ultrafiltration membrane by warm and fine for polypropylene polyvinyl alcohol blending, is will be poly-
Propylene is fine, polyvinyl alcohol and porogen are poured into equipped with the reactor of organic solvent, mechanical agitation
Mix homogeneously, standing vacuum defoamation obtains clear transparent solutions, then controls temperature at 25 DEG C, opens
The outlet valve of reactor, and into reactor in be passed through nitrogen so that the pressure in reactor is
0.2MPa, then opens spinning pump, the rotating speed controlling spinning pump in 30r/min, and by spinning
The doughnut that the spinning head of pump is extruded through 20 DEG C coagulating bath process after, by its wound on
On wind-up roll, the rotating speed of wind-up roll winding controls in 25r/min, after spinning terminates, from winding
The film of winding is taken off on roller, is placed on immersion 45h in reverse osmosis water, then is placed on
Mass percent be 50% glycerine water solution in soak 45h, then be placed on drying at room temperature and obtain
The fine hollow fiber ultrafiltration membrane of polypropylene.
Described polypropylene is fine, its with polyvinyl alcohol after the mass percent that accounts for of gross mass
For 10%, wherein the mass percent of polyvinyl alcohol be account for the warm and fine polyvinyl alcohol of polypropylene after
Total amount 13.8%；Described organic solvent, its mass percent is 85%；Described cause
Hole agent, its mass percent is 5%.
Described organic solvent is N-Methyl pyrrolidone (NMP).
Described porogen is PEG400 (PEG400).
Described cross-linking agent A is citric acid.
Described crosslinking agent B is glutaraldehyde.
Described vacuum defoamation, its vacuum is -0.09MPa.
Described preparation method, after cross-linking agent A and crosslinking agent B are grafted to ultrafiltration membrane surface,
The reverse osmosis water being 60 DEG C using temperature again cleaning treatment repeatedly.
Embodiment 2
A kind of fine hollow fiber ultrafiltration membrane preparation method of Superhydrophilic polypropylene, polypropylene is warm and fine
Polyvinyl alcohol blending prepares hollow fiber ultrafiltration membrane, and wherein polyvinyl alcohol consumption is that polypropylene is warm and fine
The 20% of the gross mass of polyvinyl alcohol consumption；Again by the hollow fiber ultrafiltration membrane preparing in quality
In the presence of percentage ratio accounts for 1% concentrated sulphuric acid, by crosslinked action by cross-linking agent A and crosslinking agent B
It is grafted to the surface of ultrafilter membrane, the consumption of wherein cross-linking agent A and crosslinking agent B is with percent mass
Respectively account for 2% than meter.
Described prepares hollow fiber ultrafiltration membrane by warm and fine for polypropylene polyvinyl alcohol blending, is will be poly-
Propylene is fine, polyvinyl alcohol and porogen are poured into equipped with the reactor of organic solvent, mechanical agitation
Mix homogeneously, standing vacuum defoamation obtains clear transparent solutions, then controls temperature at 25 DEG C, opens
The outlet valve of reactor, and into reactor in be passed through nitrogen so that the pressure in reactor is
0.2MPa, then opens spinning pump, the rotating speed controlling spinning pump in 30r/min, and by spinning
The doughnut that the spinning head of pump is extruded through 20 DEG C coagulating bath process after, by its wound on
On wind-up roll, the rotating speed of wind-up roll winding controls in 25r/min, after spinning terminates, from winding
The film of winding is taken off on roller, is placed on immersion 50h in reverse osmosis water, then is placed on
Mass percent be 50% glycerine water solution in soak 50h, then be placed on drying at room temperature and obtain
The fine hollow fiber ultrafiltration membrane of polypropylene.
Described polypropylene is fine, its with polyvinyl alcohol after the mass percent that accounts for of gross mass
For 25%, wherein the mass percent of polyvinyl alcohol be account for the warm and fine polyvinyl alcohol of polypropylene after
Total amount 20%；Described organic solvent, its mass percent is 60%；Described pore
Agent, its mass percent is 15%.
Described organic solvent is DMF (DMF).
Described porogen is PEG600 (Macrogol 600).
Described cross-linking agent A is oxalic acid.
Described crosslinking agent B is glutaraldehyde.
Described vacuum defoamation, its vacuum is -0.05MPa.
Described preparation method, after cross-linking agent A and crosslinking agent B are grafted to ultrafiltration membrane surface,
Also include the step being adopted reverse osmosis water cleaning.
Described reverse osmosis water, its temperature is 50 DEG C.
Embodiment 3
A kind of fine hollow fiber ultrafiltration membrane preparation method of Superhydrophilic polypropylene, polypropylene is warm and fine
Polyvinyl alcohol blending prepares hollow fiber ultrafiltration membrane, and wherein polyvinyl alcohol consumption is that polypropylene is warm and fine
The 15% of the gross mass of polyvinyl alcohol consumption；Again by the hollow fiber ultrafiltration membrane preparing in quality
In the presence of percentage ratio accounts for 1% concentrated sulphuric acid, by crosslinked action by cross-linking agent A and crosslinking agent B
It is grafted to the surface of ultrafilter membrane, the consumption of wherein cross-linking agent A and crosslinking agent B is with percent mass
Respectively account for 1.5% than meter.
Described prepares hollow fiber ultrafiltration membrane by warm and fine for polypropylene polyvinyl alcohol blending, is will be poly-
Propylene is fine, polyvinyl alcohol and porogen are poured into equipped with the reactor of organic solvent, mechanical agitation
Mix homogeneously, standing vacuum defoamation obtains clear transparent solutions, then controls temperature at 25 DEG C, opens
The outlet valve of reactor, and into reactor in be passed through nitrogen so that the pressure in reactor is
0.2MPa, then opens spinning pump, the rotating speed controlling spinning pump in 30r/min, and by spinning
The doughnut that the spinning head of pump is extruded through 20 DEG C coagulating bath process after, by its wound on
On wind-up roll, the rotating speed of wind-up roll winding controls in 25r/min, after spinning terminates, from winding
The film of winding is taken off on roller, is placed on immersion 48h in reverse osmosis water, then is placed on
Mass percent be 50% glycerine water solution in soak 48h, then be placed on drying at room temperature and obtain
The fine hollow fiber ultrafiltration membrane of polypropylene.
Described polypropylene is fine, its with polyvinyl alcohol after the mass percent that accounts for of gross mass
For 15%, wherein the mass percent of polyvinyl alcohol be account for the warm and fine polyvinyl alcohol of polypropylene after
Total amount 15%；Described organic solvent, its mass percent is 83%；Described pore
Agent, its mass percent is 2%.
Described organic solvent is dimethyl sulfoxide (DMSO).
Described porogen is PEG1000 (Macrogol 1000).
Described cross-linking agent A is malic acid.
Described crosslinking agent B is glutaraldehyde.
Described vacuum defoamation, its vacuum is -0.1MPa.
Described preparation method, after cross-linking agent A and crosslinking agent B are grafted to ultrafiltration membrane surface,
Also include the step being adopted reverse osmosis water cleaning.
Described reverse osmosis water, its temperature is 70 DEG C.
Embodiment 4
A kind of fine hollow fiber ultrafiltration membrane preparation method of Superhydrophilic polypropylene, polypropylene is warm and fine
Polyvinyl alcohol blending prepares hollow fiber ultrafiltration membrane, and wherein polyvinyl alcohol consumption is that polypropylene is warm and fine
The 10% of the gross mass of polyvinyl alcohol consumption；Again by the hollow fiber ultrafiltration membrane preparing in quality
In the presence of percentage ratio accounts for 1% concentrated sulphuric acid, by crosslinked action by cross-linking agent A and crosslinking agent B
It is grafted to the surface of ultrafilter membrane, the consumption of wherein cross-linking agent A and crosslinking agent B is with percent mass
Respectively account for 0.9% than meter.
Described prepares hollow fiber ultrafiltration membrane by warm and fine for polypropylene polyvinyl alcohol blending, is will be poly-
Propylene is fine, polyvinyl alcohol and porogen are poured into equipped with the reactor of organic solvent, mechanical agitation
Mix homogeneously, standing vacuum defoamation obtains clear transparent solutions, then controls temperature at 25 DEG C, opens
The outlet valve of reactor, and into reactor in be passed through nitrogen so that the pressure in reactor is
0.2MPa, then opens spinning pump, the rotating speed controlling spinning pump in 30r/min, and by spinning
The doughnut that the spinning head of pump is extruded through 20 DEG C coagulating bath process after, by its wound on
On wind-up roll, the rotating speed of wind-up roll winding controls in 25r/min, after spinning terminates, from winding
The film of winding is taken off on roller, is placed on immersion 46h in reverse osmosis water, then is placed on
Mass percent be 50% glycerine water solution in soak 49h, then be placed on drying at room temperature and obtain
The fine hollow fiber ultrafiltration membrane of polypropylene.
Described polypropylene is fine, its with polyvinyl alcohol after the mass percent that accounts for of gross mass
For 20%, wherein the mass percent of polyvinyl alcohol be account for the warm and fine polyvinyl alcohol of polypropylene after
Total amount 5%；Described organic solvent, its mass percent is 71%；Described porogen,
Its mass percent is 9%.
Described organic solvent is N,N-dimethylacetamide (DMAC).
Described porogen is PVPK80(Polyvinylpyrrolidone k80).
Described cross-linking agent A is tartaric acid.
Described crosslinking agent B is glutaraldehyde.
Described vacuum defoamation, its vacuum is -0.08MPa.
Described preparation method, after cross-linking agent A and crosslinking agent B are grafted to ultrafiltration membrane surface,
Also include the step being adopted reverse osmosis water cleaning.
Described reverse osmosis water, its temperature is 55 DEG C.
Embodiment 5
A kind of fine hollow fiber ultrafiltration membrane preparation method of Superhydrophilic polypropylene, polypropylene is warm and fine
Polyvinyl alcohol blending prepares hollow fiber ultrafiltration membrane, and wherein polyvinyl alcohol consumption is that polypropylene is warm and fine
The 7% of the gross mass of polyvinyl alcohol consumption；Again by the hollow fiber ultrafiltration membrane preparing in quality
In the presence of percentage ratio accounts for 1% concentrated sulphuric acid, by crosslinked action by cross-linking agent A and crosslinking agent B
It is grafted to the surface of ultrafilter membrane, the consumption of wherein cross-linking agent A and crosslinking agent B is with percent mass
Respectively account for 0.09% than meter.
Described prepares hollow fiber ultrafiltration membrane by warm and fine for polypropylene polyvinyl alcohol blending, is will be poly-
Propylene is fine, polyvinyl alcohol and porogen are poured into equipped with the reactor of organic solvent, mechanical agitation
Mix homogeneously, standing vacuum defoamation obtains clear transparent solutions, then controls temperature at 25 DEG C, opens
The outlet valve of reactor, and into reactor in be passed through nitrogen so that the pressure in reactor is
0.2MPa, then opens spinning pump, the rotating speed controlling spinning pump in 30r/min, and by spinning
The doughnut that the spinning head of pump is extruded through 20 DEG C coagulating bath process after, by its wound on
On wind-up roll, the rotating speed of wind-up roll winding controls in 25r/min, after spinning terminates, from winding
The film of winding is taken off on roller, is placed on immersion 47h in reverse osmosis water, then is placed on
Mass percent be 50% glycerine water solution in soak 48h, then be placed on drying at room temperature and obtain
The fine hollow fiber ultrafiltration membrane of polypropylene.
Described polypropylene is fine, its with polyvinyl alcohol after the mass percent that accounts for of gross mass
For 25%, wherein the mass percent of polyvinyl alcohol be account for the warm and fine polyvinyl alcohol of polypropylene after
Total amount 7%；Described organic solvent, its mass percent is 60%；Described porogen,
Its mass percent is 15%.
Described organic solvent is dimethyl sulfoxide (DMSO).
Described porogen is lithium chloride (LiCl).
Described cross-linking agent A is citric acid.
Described crosslinking agent B is glutaraldehyde.
Described vacuum defoamation, its vacuum is -0.07MPa.
Described preparation method, after cross-linking agent A and crosslinking agent B are grafted to ultrafiltration membrane surface,
Also include the step being adopted reverse osmosis water cleaning.
Described reverse osmosis water, its temperature is 65 DEG C.
Claims (10)
1. the fine hollow fiber ultrafiltration membrane preparation method of a kind of Superhydrophilic polypropylene, its feature exists
In by warm and fine for polypropylene polyvinyl alcohol blending preparation hollow fiber ultrafiltration membrane, wherein polyvinyl alcohol
Consumption is the 2-20% of the gross mass of polypropylene warm and fine polyvinyl alcohol consumption；In preparing again
In the presence of fibre ultrafiltration film accounts for 1% concentrated sulphuric acid in mass percent, by crosslinked action
Cross-linking agent A and crosslinking agent B are grafted to the surface of ultrafilter membrane, wherein cross-linking agent A and crosslinking agent B
Consumption be respectively to account for 0.05-2% by percentage to the quality.
2. Superhydrophilic polypropylene as claimed in claim 1 fine hollow fiber ultrafiltration membrane preparation side
Method is it is characterised in that described prepare doughnut by warm and fine for polypropylene polyvinyl alcohol blending and surpass
Filter membrane, is the reactor poured fine for polypropylene, polyvinyl alcohol and porogen into equipped with organic solvent
Interior, mechanical agitation mix homogeneously, standing vacuum defoamation obtains clear transparent solutions, then controls temperature
At 25 DEG C, open the outlet valve of reactor, and into reactor in be passed through nitrogen so that reaction
Pressure in kettle is 0.2MPa, then opens spinning pump, controls the rotating speed of spinning pump to exist
30r/min, and the doughnut that the spinning head of spinning pump is extruded is at 20 DEG C of coagulating bath
After reason, by it on wind-up roll, the rotating speed of wind-up roll winding controls in 25r/min, waits to spin
The film of winding, after silk terminates, is taken off from wind-up roll, is placed in reverse osmosis water and soaks
45-50h, then it is placed on immersion 45-50h in the glycerine water solution that mass percent is 50%,
It is placed on drying at room temperature again and obtain the fine hollow fiber ultrafiltration membrane of polypropylene.
3. Superhydrophilic polypropylene as claimed in claim 2 fine hollow fiber ultrafiltration membrane preparation side
It is characterised in that described polypropylene is fine, it is accounted for method with the gross mass after polyvinyl alcohol
Mass percent be 10-25%, wherein the mass percent of polyvinyl alcohol is that to account for polypropylene warm and fine
The 2-20% of the total amount after polyvinyl alcohol；Described organic solvent, its mass percent is
60-85%；Described porogen, its mass percent is 2-15%.
4. the fine hollow fiber ultrafiltration membrane system of Superhydrophilic polypropylene as claimed in claim 2 or claim 3
Preparation Method it is characterised in that described organic solvent be N-Methyl pyrrolidone (NMP),
DMF (DMF), N,N-dimethylacetamide (DMAC), diformazan
Any one of base sulfoxide (DMSO).
5. the fine hollow fiber ultrafiltration membrane system of Superhydrophilic polypropylene as claimed in claim 2 or claim 3
Preparation Method it is characterised in that described porogen be PEG400 (PEG400),
PEG600 (Macrogol 600), PEG1000 (Macrogol 1000), PEG2000 are (poly-
Ethylene glycol 2000), PEG6000 (polyethylene glycol 6000), PEG10000 (Polyethylene Glycol
10000)、PVPK15(Polyvinylpyrrolidone K15), PVPK30(Polyvinylpyrrolidone
K30)、PVPK40(Polyvinylpyrrolidone k40), PVPK60(Polyvinylpyrrolidone k60),
PVPK80(Polyvinylpyrrolidone k80), PVPk90(PVP K90) or chlorine
Any one of change lithium (LiCl).
6. Superhydrophilic polypropylene as claimed in claim 1 fine hollow fiber ultrafiltration membrane preparation side
Method is it is characterised in that described cross-linking agent A is citric acid, oxalic acid, malic acid, tartaric acid
In any one.
7. Superhydrophilic polypropylene as claimed in claim 1 fine hollow fiber ultrafiltration membrane preparation side
Method is it is characterised in that described crosslinking agent B is glutaraldehyde.
8. Superhydrophilic polypropylene as claimed in claim 2 fine hollow fiber ultrafiltration membrane preparation side
It is characterised in that described vacuum defoamation, its vacuum is -0.05～-0.1MPa to method.
9. Superhydrophilic polypropylene as claimed in claim 1 fine hollow fiber ultrafiltration membrane preparation side
Method, it is characterised in that described preparation method, cross-linking agent A and crosslinking agent B is being grafted to
After ultrafiltration membrane surface, also include the step being adopted reverse osmosis water cleaning.
10. Superhydrophilic polypropylene as claimed in claim 1 fine hollow fiber ultrafiltration membrane preparation
It is characterised in that described reverse osmosis water, its temperature is 50-70 DEG C to method.
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| CN109692577A (en) * | 2017-10-20 | 2019-04-30 | 宁波方太厨具有限公司 | The cross-linking modified preparation method of total coating of hollow fiber ultrafiltration membrane |
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