CN105457510B - A kind of hydrophilic polyethersulfone milipore filter and preparation method thereof - Google Patents
A kind of hydrophilic polyethersulfone milipore filter and preparation method thereof Download PDFInfo
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- CN105457510B CN105457510B CN201410456602.8A CN201410456602A CN105457510B CN 105457510 B CN105457510 B CN 105457510B CN 201410456602 A CN201410456602 A CN 201410456602A CN 105457510 B CN105457510 B CN 105457510B
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- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 46
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004088 foaming agent Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 8
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 58
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 13
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical group O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 10
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- 238000001223 reverse osmosis Methods 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000011265 semifinished product Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- 238000001764 infiltration Methods 0.000 claims description 4
- 229960003511 macrogol Drugs 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
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000008118 PEG 6000 Substances 0.000 claims description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 claims description 2
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920003081 Povidone K 30 Polymers 0.000 claims description 2
- 229920003082 Povidone K 90 Polymers 0.000 claims description 2
- 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 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 230000008595 infiltration Effects 0.000 claims description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- IQXJCCZJOIKIAD-UHFFFAOYSA-N 1-(2-methoxyethoxy)hexadecane Chemical compound CCCCCCCCCCCCCCCCOCCOC IQXJCCZJOIKIAD-UHFFFAOYSA-N 0.000 claims 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 claims 1
- 229950009789 cetomacrogol 1000 Drugs 0.000 claims 1
- 150000004040 pyrrolidinones Chemical class 0.000 claims 1
- 239000012528 membrane Substances 0.000 abstract description 35
- 238000013019 agitation Methods 0.000 abstract description 3
- 230000010148 water-pollination Effects 0.000 abstract description 3
- 210000004379 membrane Anatomy 0.000 description 20
- 238000000034 method Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 8
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical group OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002464 physical blending Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 210000002469 basement membrane Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000002894 organic compounds Chemical group 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Abstract
The present invention relates to technical field of membrane, especially a kind of hydrophilic polyethersulfone milipore filter and preparation method thereof；Its composition includes：Polyether sulfone, polyvinyl alcohol, organic solvent, pore-foaming agent, crosslinking agent A, crosslinking agent B；Preparation method：Polyether sulfone and polyvinyl alcohol are dissolved in organic solvent, pore-foaming agent is then added, mechanical agitation is carried out and is sufficiently mixed uniformly, stand vacuum defoamation and obtain clear transparent solutions；Solution is placed on non-woven fabrics again and carries out knifing, in the presence of mass percent is 1% sulfuric acid, crosslinking agent A and crosslinking agent B are grafted to by ultrafiltration membrane surface by cross-linking reaction, milipore filter is made, with preferable resistance tocrocking, hydrophily, temperature tolerance and higher durability；Its film properties is stable, hydrophilic layer is not easily runed off.
Description
Technical field
The present invention relates to technical field of membrane, especially a kind of hydrophilic polyethersulfone milipore filter and preparation method thereof.
Background technology
Milipore filter is one of polymeric membrane for separation for developing earliest, the sixties ultrafiltration apparatus be achieved that industrialization.Quilt
It is widely used in the various isolation and purification processes of the industries such as electronics, chemical industry, medicine, food.But the problem of filter membrane pollutes still seems
Than more prominent, many experts and scholars have done substantial amounts of research work on the problem of filter membrane pollutes is solved, it is believed that increase film surface
Hydrophily be improve film resistance tocrocking a kind of very effective method, directly made including the material using good hydrophilic property
Film is carried out hydrophilically modified to ultrafiltration membrane surface.Such as Patent No. CN201210247267.1《A kind of hydrophilic ultrafiltration membrane
Preparation method》Contain Fe by being introduced in casting solution3+、Al3+Prepare and be effectively improved and stable milipore filter etc. high price metal salt
Hydrophilicity, solve in the prior art hydrophilic additive be easy to run off, skewness the problem of.
And hydrophilic modification method main at present includes surface coating, surface grafting and physical blending etc..Surface is coated
It is that the surface of hydrophobic membrane is applied into last layer hydrophilic polymer, being then heat-treated or be chemically treated fixes coating, this side
The main defect of method is that coat is unstable, is easy to come off at high temperature.Surface grafting is under certain conditions, in hydrophobic membrane
Surface introduces hydrophilic radical, and to change the surface nature of hydrophobic membrane, mainly surface chemical reaction can make modified monomer with surpassing
Chemical bond is formed between filter membrane, it is more with practical value.But often lacking in the ultrafiltration membrane material used at present is used for into one
The active group of reaction is walked, therefore, it is difficult to chemically reacted.Mainly hydroaropic substance and polymer are blended for physical blending,
By adding the macromolecule modified thing with active group in casting solution, and milipore filter is prepared by immersion precipitation, then
Ultrafiltration membrane surface is modified again.Therefore, having substantial amounts of researcher from this angle, larger exploration is made that to filter membrane
And thinking, and then obtain more technical scheme.Such as Patent No. CN201310539041.3《Novel water filtering ultrafiltration
Film》Using sulfonated polyether sulfone, SO4 2-Negatively charged grade is that material prepares the milipore filter with the features such as efficient, purifying rate is high,
While ensureing to remove harmful substance, retain to mineral matter necessary to human body, being adapted to the large area at a variety of industrial water sources makes
With.And for example Patent No. CN200710037396.7《Method for preparing hydrophilic low catching molecular composite ultrafiltering membrane》Using poly-
Sulfone or polyether sulfone are membrane material, by the use of layer upon layer electrostatic self-assembling technique milipore filter basement membrane over-assemble polyelectrolyte multilayer film as
Composite bed, thus prepare surface charge and electrically controllable, surface structure is controllable, have good rejection to low molecular weight solutes
Can, while having the composite hyperfiltration membrane of preferable antifouling property.
As can be seen here, the technical scheme of milipore filter in the prior art and preparation method thereof is also difficult to meet many performances
Demand, and be only to go to meet the properties of milipore filter in terms of single；Therefore, so that after using ultrafiltration membrance filter, all the time
Be difficult to obtain more excellent water quality, then, this researcher through efforts of many years with exploration, be milipore filter and its prepare neck
Domain provides a kind of new approaches.
The content of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of hydrophilic polyethersulfone milipore filter
And preparation method thereof, it has the features such as durable, performance is stable, hydrophilic layer is not easily runed off.
It is achieved particular by following technical scheme：
A kind of hydrophilic polyethersulfone milipore filter, it is characterised in that：Raw material quality number is respectively 10-25 parts of polyether sulfone,
0.05-2 parts of polyvinyl alcohol, 60-85 parts of organic solvent, 2-15 parts of pore-foaming agent, A0.05-2 parts of crosslinking agent, crosslinking agent B 0.05-2
Part.
Described material quality number is respectively 15 parts of polyether sulfone, 1 part of polyvinyl alcohol, 70 parts of organic solvent, pore-foaming agent 11
Part, A1.5 parts of crosslinking agent, 1.5 parts of crosslinking agent B.
Described organic solvent is 1-METHYLPYRROLIDONE (NMP), N,N-dimethylformamide (DMF), N, N- dimethyl
Acetamide (DMAC), dimethyl sulfoxide (DMSO) (DMSO) it is any.
The pore-foaming agent is PEG400 (polyethylene glycol 400), PEG600 (Macrogol 600), PEG1000 (polyethylene glycol
1000), PEG2000 (polyethylene glycol 2000), PEG6000 (Macrogol 6000), PEG10000 (PEG20000),
PVPK15(polyvinylpyrrolidone K15), PVPK30(PVP K30), PVPK40(polyvinylpyrrolidone k40),
PVPK60(polyvinylpyrrolidone k60), PVPK80(polyvinylpyrrolidone k80), PVPk90(PVP K90) and
Lithium chloride (LiCl) it is any.
The crosslinking agent A is any one of citric acid, oxalic acid, malic acid, tartaric acid.
The crosslinking agent B is glutaraldehyde.
A kind of preparation method of hydrophilic polyethersulfone milipore filter, comprises the following steps：
(1) polyether sulfone and polyvinyl alcohol are dissolved in organic solvent successively according to above-mentioned mass parts, and use agitator
After stirring, the pore-foaming agent of above-mentioned mass parts is added, and continues to be uniformly mixed using agitator, is stood after 12-24h,
Vacuum defoamation is carried out to mixed liquor, clear transparent solutions are obtained.
(2) by step 1) clear transparent solutions that obtain are placed on non-woven fabrics and carry out knifing, then it is placed on 60-80 DEG C of water
Middle reverse-osmosis treated 10-20h.
(3) by step 2) obtain milipore filter just finished product be placed in concentration be 1% sulfuric acid in, add thereto successively above-mentioned
The crosslinking agent A and crosslinking agent B of mass parts, and then finished product at the beginning of crosslinking agent A and crosslinking agent B are grafted into milipore filter by cross-linking reaction
Surface, obtain milipore filter semi-finished product.
(4) by step 3) the milipore filter semi-finished product that obtain are placed in 50-70 DEG C of water after reverse-osmosis treated 1-5 times, every time
Anti-penetration wastewater disposal 3-7min, you can milipore filter is made.
Described agitator stirring is mechanical agitation, and its mixing speed is 80-100r/min.
The vacuum of described vacuum defoamation is 0.02-0.08MPa.
It with finished product at the beginning of milipore filter according to mass ratio is (1-2.3) that the amount of 1% described sulfuric acid, which is,:(0.9-1.3)；Described
The time of vacuum defoamation is 10-30min.
Above-mentioned polyether sulfone used is the thermoplastic macromolecule material of a kind excellent combination property；It has excellent resistance to
Hot property, physical and mechanical properties, insulating properties etc., particularly with continuously can drastically changing using and temperature at high temperature
Environment in remain to the outstanding advantages such as retention property is stable.
Polyvinyl alcohol described above is organic compound, white plates, cotton-shaped or pulverulent solids, it is tasteless, be dissolved in water,
It is slightly soluble in dimethyl sulfoxide (DMSO).
Non-woven fabrics described above, refers to non-woven cloth, or be adhesive-bonded fabric.It is formed by one kind need not spin cotton and weave cloth
Textile staple or long filament, are simply oriented by fabric or support is arranged at random, form fibre net structure, then using machinery, heat
The methods such as viscous or chemistry are reinforced and formed.
Knifing described above is exactly to coat layer of substance in certain base material surface.
Cross-linking reaction described above, refers to the linear polymeric with certain degree of polymerization under the crosslinked action of crosslinking agent
Carry out cross-linking reaction so that linear polymeric is interconnected to form the network structure macromolecule with certain crosslink density.
Counter-infiltration described above, refer to infiltration a kind of reverse travel motion, be one kind under pressure-driven by means of
The separation method that the selective retention effect of pellicle separates the solute in solution and solvent, its aperture is about in 5~10A.It
The purification and concentration of various liquid are widely used in, wherein most common application example is in water treatment technology, to use reverse osmosis
Saturating technology can remove the impurity such as the inorganic ions in raw water, bacterium, virus, organic matter and colloid, high-quality pure to obtain
Water purification.
Compared with prior art, the invention has the advantages that and technique effect：
1. by the way that polyether sulfone and polyvinyl alcohol are dissolved in organic solvent successively, and after being stirred using agitator,
Pore-foaming agent is added, and by carrying out vacuum defoamation to mixed liquor, obtains clear transparent solutions, the clear transparent solutions is placed in nothing
Spin and carry out knifing on cloth, and in the presence of sulfuric acid, crosslinking agent A and crosslinking agent B are subjected to cross-linking reaction so that make what is come
Film has the features such as preferable durability, performance stabilization.
2. by carrying out research and discussion with supermembrane flow is produced to each raw material quality number dosage, having drawn to expire
The supermembrane of many performance requirements of foot, overcomes and the properties for meeting milipore filter is removed in terms of single, reduce the wave to raw material
Take, reduce the use cost of membrane technology, improve the performance of membrane material, the further perfect technology in film field.
3. by the way that pore-foaming agent is added in the organic solvent that polyether sulfone and polyvinyl alcohol dissolve so that mixed solution is rapid
Diffuse to form poroid, and then improve the situation of mixed solution skewness on non-woven fabrics during knifing, and pass through addition
Mass percent is that 1% sulfuric acid carries out cross-linking reaction, crosslinking agent A and crosslinking agent B is grafted into ultrafiltration membrane surface, so as to obtain
With the milipore filter that stain resistance is strong, hydrophilic layer is not easily runed off.
Embodiment
The present invention is specifically described below by embodiment.It is necessarily pointed out that the present embodiment is served only for pair
Invention is described further and understood, is not limiting the scope of the invention, if those skilled in the art is according to upper
The modifications and adaptations that present invention makes some non-prominent essential characteristics and non-significant progress to the present invention are stated, are still belonged to
In the scope of the present invention.
Embodiment 1
A kind of hydrophilic polyethersulfone milipore filter, its raw material is polyether sulfone 15kg, polyvinyl alcohol 0.05kg, dimethyl sulfoxide (DMSO)
(DMSO) it is 82.95kg, PEG400 (polyethylene glycol 400) is 2kg, and citric acid is 0.05kg, and glutaraldehyde is 0.05kg.
Its specific preparation method, comprises the following steps：
(1) polyether sulfone and polyvinyl alcohol are dissolved in organic solvent successively according to above-mentioned mass parts, and use agitator
After stirring, the pore-foaming agent of above-mentioned mass parts is added, and continues to be uniformly mixed using agitator, is stood after 12h, to mixed
Close liquid and carry out vacuum defoamation, obtain clear transparent solutions.
(2) by step 1) clear transparent solutions that obtain are placed on non-woven fabrics and carry out knifing, then be placed in 60 DEG C of water
Reverse-osmosis treated 15h.
(3) by step 2) obtain milipore filter just finished product be placed in concentration be 1% sulfuric acid in, add thereto successively above-mentioned
The citric acid and glutaraldehyde of mass parts, and then the table of finished product at the beginning of citric acid and glutaraldehyde are grafted into milipore filter by cross-linking reaction
Face, obtains milipore filter semi-finished product.
(4) by step 3) the milipore filter semi-finished product that obtain are placed in 50 DEG C of water after reverse-osmosis treated 5 times, each counter-infiltration
Water process 3min, you can milipore filter is made.
Agitator stirring therein is mechanical agitation, and its mixing speed is 80r/min；The vacuum of vacuum defoamation is
0.02MPa；It with finished product at the beginning of milipore filter according to mass ratio is 1 that the amount of the concentrated sulfuric acid, which is,:0.9；The time of vacuum defoamation is 10min.
Detected by the performance of the milipore filter to acquisition：It has the performance that resistance tocrocking, hydrophilic layer are not easily runed off.
Embodiment 2
A kind of hydrophilic polyethersulfone milipore filter, on the basis of embodiment 1, other preparation method step be the same as Examples 1, its
Raw material is polyether sulfone 20kg, and polyvinyl alcohol 0.05kg, dimethyl sulfoxide (DMSO) (DMSO) is 77.95kg, PEG400 (polyethylene glycol 400)
For 2kg, citric acid is 1kg, and glutaraldehyde is 1kg.
Embodiment 3
A kind of hydrophilic polyethersulfone milipore filter, on the basis of embodiment 1, other preparation method step be the same as Examples 1, its
Raw material is polyether sulfone 18kg, and polyvinyl alcohol 0.05kg, dimethyl sulfoxide (DMSO) (DMSO) is 79.95kg, PEG400 (polyethylene glycol 400)
For 2kg, citric acid is 0.05kg, and glutaraldehyde is 1kg.
Embodiment 4
A kind of hydrophilic polyethersulfone milipore filter, on the basis of embodiment 1, other preparation method step be the same as Examples 1, its
Raw material is polyether sulfone 18kg, and polyvinyl alcohol 2kg, dimethyl sulfoxide (DMSO) (DMSO) is 78kg, and PEG400 (polyethylene glycol 400) is 2kg,
Citric acid is 0.05kg, and glutaraldehyde is 0.05kg.
Embodiment 5
A kind of hydrophilic polyethersulfone milipore filter, on the basis of embodiment 1, other preparation method step be the same as Examples 1, its
Raw material is polyether sulfone 15kg, and polyvinyl alcohol 2kg, dimethyl sulfoxide (DMSO) (DMSO) is 81kg, and PEG400 (polyethylene glycol 400) is 2kg,
Citric acid is 0.05kg, and glutaraldehyde is 1kg.
Embodiment 6
A kind of hydrophilic polyethersulfone milipore filter, on the basis of embodiment 1, other preparation method step be the same as Examples 1, its
Raw material is polyether sulfone 18kg, and polyvinyl alcohol 2kg, dimethyl sulfoxide (DMSO) (DMSO) is 80kg, and PEG400 (polyethylene glycol 400) is
10kg, citric acid is 1kg, and glutaraldehyde is 1kg.
Embodiment 7
A kind of hydrophilic polyethersulfone milipore filter, on the basis of embodiment 1, other preparation method step be the same as Examples 1, its
Raw material is polyether sulfone 20kg, and polyvinyl alcohol 1kg, dimethyl sulfoxide (DMSO) (DMSO) is 82kg, and PEG400 (polyethylene glycol 400) is
11kg, citric acid is 1kg, and glutaraldehyde is 1kg.
Test example：
The properties and properties carry out group having below by tests below example come the milipore filter to the present invention
Index after conjunction is detected, is specifically：
The hydrophilicity experiment of experimental example 1
1.1 test material
Ten size identical uncovered cups, clear water, the milipore filter of the embodiment of the present invention 1, documents
CN200710037396.7's《Method for preparing hydrophilic low catching molecular composite ultrafiltering membrane》Obtained product composite hyperfiltration membrane
It is used as test control group.Five groups of A, B, C, D, E is denoted as, check experiment is carried out.
1.2 test method
Take ten cups (500ml), two one group, be divided into five groups, every group of cup one and be used for placing of the invention real
The milipore filter numbering for applying example 1 is 1, and another is placed by documents CN200710037396.7's《Hydrophilic low catching molecule
Measure Compound Ultrafiltration membrane preparation method》Obtained composite hyperfiltration membrane numbering is 2.And for the weight point for the two kinds of milipore filters tested
Wei not 40g, the surface area (cm for two kinds of milipore filters of experiment2) all it is 5*5=25cm2, consistency of thickness.It will be made by specification
Milipore filter be comparatively placed in ten cups, into each cup 250ml clear water carry out 5 minutes test.
1.3 experimental result
The milipore filter taken out in each cup is weighed, and its weight is respectively shown in table 1：
Hydrophilic experiment (the unit of table 1：g)
As seen from the above table, the hydrophily of the made hydrophilic polyethersulfone milipore filter of the present embodiment 1 is preferable, and hydrophilicity
It is evenly distributed, than existing hydrophilic low catching molecular composite ultrafiltering membrane effect preferably, with significant effect.
The stain resistance of experimental example 2 not easily runs off by force experiment with hydrophilic layer
2.1 experiment material
Sanitary sewage (filtering block larger material) some, milipore filter of the embodiment of the present invention 1, documents
CN201010210573.9's《The method for preparing Hydrophilized porous membrane》The perforated membrane of system is as test control group, two length
0.5m, bore are 10cm identical water pipe.Two longer thin wires.
2.2 test method
Two kinds of above-mentioned supermembrane materials are divided into surface area (cm respectively2) it is 15*15=225cm2, covered with milipore filter
One end of water pipe, filter membrane is fixed with thin wire, is made to form an entirety between milipore filter and water pipe, is obtained a filter membrane mistake
Filter, one end for having film is the low side of filter, and the one end for there be not film is top.Two kinds of filter membranes are divided according to methods described above
It is not fixed on two water pipes, obtains two membrane filters.Two filters of gained are individually placed to surface water plane into 15 °
The length and width at angle is respectively above 0.6m, 0.5m plank, and two filter membrane devices top upward, bottom is down, and placed side by side.
Then by some sewage continuously, be introduced into identical water in two filters, when a length of 10 days.
2.3 experimental result
After experiment terminates, the milipore filter hydrophilic layer that the present embodiment 1 is made is almost intact, and hydrophilic layer is not destroyed, and is illustrated
Its film properties is stable；And it is very limpid by the sewage of this filter, with existing file CN201010210573.9's《Prepare parent
The method of aqueous perforated membrane》The perforated membrane of system, which is compared, significant effect.
Herein it is important to point out that, above example and test example are only limitted to the technology effect to technical scheme
Fruit is further to be explained, it is impossible to is interpreted as further to technical scheme and is limited, those skilled in the art exist
The substantive distinguishing features for the non-protruding made on the basis of this and the improvement of marked improvement, still fall within the protection category of the present invention.
Claims (9)
1. a kind of hydrophilic polyethersulfone milipore filter, it is characterised in that：Raw material quality number is respectively 10-25 parts of polyether sulfone, is gathered
0.05-2 parts of vinyl alcohol, 60-85 parts of organic solvent, 2-15 parts of pore-foaming agent, A0.05-2 parts of crosslinking agent, 0.05-2 parts of crosslinking agent B；
The preparation method of hydrophilic polyethersulfone milipore filter, comprises the following steps：
(1) polyether sulfone and polyvinyl alcohol are dissolved in organic solvent successively according to above-mentioned mass parts, and using agitator stirring
After uniform, the pore-foaming agent of above-mentioned mass parts is added, and continues to be uniformly mixed using agitator, is stood after 12-24h, to mixed
Close liquid and carry out vacuum defoamation, obtain clear transparent solutions；
(2) by step 1) clear transparent solutions that obtain are placed on non-woven fabrics and carry out knifing, then be placed in 60-80 DEG C of water anti-
Infiltration processing 10-20h；
(3) by step 2) obtain milipore filter just finished product be placed in concentration be 1% sulfuric acid in, add above-mentioned quality thereto successively
Part crosslinking agent A and crosslinking agent B, and then the table of finished product at the beginning of crosslinking agent A and crosslinking agent B are grafted into milipore filter by cross-linking reaction
Face, obtains milipore filter semi-finished product；
(4) by step 3) the milipore filter semi-finished product that obtain are placed in 50-70 DEG C of water after reverse-osmosis treated 1-5 times, each reverse osmosis
Permeable processing 3-7min, you can milipore filter is made.
2. hydrophilic polyethersulfone milipore filter as claimed in claim 1, it is characterised in that：Described material quality number is respectively
15 parts of polyether sulfone, 1 part of polyvinyl alcohol, 70 parts of organic solvent, 11 parts of pore-foaming agent, A1.5 parts of crosslinking agent, 1.5 parts of crosslinking agent B.
3. hydrophilic polyethersulfone milipore filter as claimed in claim 1 or 2, it is characterised in that：Described organic solvent is N- first
Base pyrrolidones (NMP), N,N-dimethylformamide (DMF), DMAC N,N' dimethyl acetamide (DMAC), dimethyl sulfoxide (DMSO) (DMSO)
It is any.
4. hydrophilic polyethersulfone milipore filter as claimed in claim 1 or 2, it is characterised in that：The pore-foaming agent is PEG400 (poly-
Ethylene glycol 400), PEG600 (Macrogol 600), PEG1000 (cetomacrogol 1000), PEG2000 (polyethylene glycol 2000),
PEG6000 (Macrogol 6000), PEG10000 (PEG20000), PVPK15(polyvinylpyrrolidone K15), PVPK30
(PVP K30), PVPK40(polyvinylpyrrolidone k40), PVPK60(polyvinylpyrrolidone k60), PVPK80
(polyvinylpyrrolidone k80), PVPk90(PVP K90) and lithium chloride (LiCl) it is any.
5. hydrophilic polyethersulfone milipore filter as claimed in claim 1 or 2, it is characterised in that：The crosslinking agent A be citric acid,
Any one of oxalic acid, malic acid, tartaric acid.
6. hydrophilic polyethersulfone milipore filter as claimed in claim 1 or 2, it is characterised in that：The crosslinking agent B is glutaraldehyde.
7. hydrophilic polyethersulfone milipore filter as claimed in claim 1, it is characterised in that：Described agitator stirring is stirred for machinery
Mix, and its mixing speed is 80-100r/min.
8. hydrophilic polyethersulfone milipore filter as claimed in claim 1, it is characterised in that：The vacuum of described vacuum defoamation is
0.02-0.08MPa。
9. hydrophilic polyethersulfone milipore filter as claimed in claim 1, it is characterised in that：The amount of 1% described sulfuric acid and ultrafiltration
Just finished product is (1-2.3) according to mass ratio to film:(0.9-1.3)；The time of described vacuum defoamation is 10-30min.
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| CN106268371A (en) * | 2016-08-08 | 2017-01-04 | 贵阳时代沃顿科技有限公司 | A kind of polyacrylonitrile hollow fiber ultrafilter membrane and preparation method thereof |
| CN106422819A (en) * | 2016-09-26 | 2017-02-22 | 天津华清健坤膜科技有限公司 | Ultrafiltration membrane using PVA for improving hydrophilic property and preparation method of the ultrafiltration membrane |
| CN106914154A (en) * | 2017-02-27 | 2017-07-04 | 武汉科技大学 | PEG‑TiO2The preparation method of the hydrophilic milipore filters of/PES/PVA and application |
| EP3756753B1 (en) * | 2019-06-27 | 2022-08-31 | Sartorius Stedim Biotech GmbH | Combination of pyrrolidone based solvents for the production of porous membranes |
| CN111389226B (en) * | 2020-04-17 | 2022-07-05 | 浙江理工大学 | Permanent hydrophilic ultrafiltration membrane and preparation method thereof |
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| CN101559327A (en) * | 2009-05-08 | 2009-10-21 | 东华大学 | Nanometre-sized fibre liquid separation composite film and preparation method thereof |
| CN103331108A (en) * | 2013-07-12 | 2013-10-02 | 中国能源建设集团安徽省电力设计院 | Polymer pervaporation membrane prepared by dialysis method after membrane formation and preparation method of polymer pervaporation membrane |
| CN103331109A (en) * | 2013-07-16 | 2013-10-02 | 长春工业大学 | Preparation method of hyperbranched polyester-polyvinyl alcohol pervaporation membrane |
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| CN101559327A (en) * | 2009-05-08 | 2009-10-21 | 东华大学 | Nanometre-sized fibre liquid separation composite film and preparation method thereof |
| CN103331108A (en) * | 2013-07-12 | 2013-10-02 | 中国能源建设集团安徽省电力设计院 | Polymer pervaporation membrane prepared by dialysis method after membrane formation and preparation method of polymer pervaporation membrane |
| CN103331109A (en) * | 2013-07-16 | 2013-10-02 | 长春工业大学 | Preparation method of hyperbranched polyester-polyvinyl alcohol pervaporation membrane |
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