A kind of hydrophilic polyethersulfone milipore filter and preparation method thereof
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 developed the earliest, the sixties ultrafiltration apparatus just achieve industrialization.Be widely used in the various isolation and purification processes of the industries such as electronics, chemical industry, medicine, food.But the problem that filter membrane pollutes still seems more outstanding, a lot of experts and scholars have done a large amount of research work in the problem solving filter membrane pollution, think that the hydrophily increasing film surface improves the very effective method of one of film resistance tocrocking, comprising utilizing the direct masking of the material of good hydrophilic property or carrying out hydrophilically modified to ultrafiltration membrane surface.If the patent No. is that CN201210247267.1 " a kind of preparation method of hydrophilic ultrafiltration membrane " by introducing containing Fe in casting solution
3+, Al
3+prepare and effectively improve Deng high price slaine and stablize that hydrophilic additive in the hydrophilicity of milipore filter, solution prior art easily runs off, problem pockety.
And hydrophilic modification method main at present comprises surface coating, surface grafting and physical blending etc.Surface coating is that the surface of hydrophobic membrane is coated with last layer hydrophilic polymer, then heat-treats or chemical treatment makes coating fix, and the main defect of this method is that coat is unstable, is at high temperature easy to come off.Surface grafting is under certain conditions, and introduce hydrophilic radical on hydrophobic membrane surface, change the surface nature of hydrophobic membrane, mainly surface chemical reaction can make to form chemical bond between modified monomer and milipore filter, has more practical value.But often lack the active group being used for reaction further in the ultrafiltration membrane material used at present, be therefore difficult to carry out chemical reaction.Physical blending, mainly by hydroaropic substance and polyblend, by adding the macromolecule modified thing with active group in casting solution, and is prepared milipore filter by immersion precipitation, and then is modified ultrafiltration membrane surface.For this reason, have a large amount of researchers from then on angle set out, larger exploration and thinking have been made to filter membrane, and then have obtained more technical scheme." Novel ultrafiltration membrane for water filtration " that be CN201310539041.3 as the patent No. adopts sulfonated polyether sulfone, SO
4 2-electronegative grade is that material is prepared and had milipore filter that is efficient, purifying rate high, and while harmful substance is removed in guarantee, retain the necessary mineral matter of human body, the large area being applicable to multiple industrial water source uses.And for example the patent No. is that " method for preparing hydrophilic low catching molecular composite ultrafiltering membrane " of CN200710037396.7 adopts polysulfones or polyether sulfone to be membrane material, utilize layer upon layer electrostatic self-assembling technique to assemble polyelectrolyte multilayer film as composite bed on milipore filter basement membrane, thus prepare surface charge and electrically controlled, surface structure is controlled, the composite hyperfiltration membrane that low molecular weight solutes had to good cutoff performance, have good antifouling property simultaneously.
As can be seen here, the technical scheme of milipore filter in the prior art and preparation method thereof is also difficult to the demand meeting many performances, and is only the properties removing to meet milipore filter from single aspect; For this reason, make to adopt after ultrafiltration membrance filter, be difficult to all the time obtain comparatively excellent water quality, so, this researcher through efforts of many years with exploration, for milipore filter and preparation field thereof provide a kind of new approaches.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the invention provides a kind of hydrophilic polyethersulfone milipore filter and preparation method thereof, the feature such as it has durable, stable performance, hydrophilic layer not easily runs off.
Be achieved particular by following technical scheme:
A kind of hydrophilic polyethersulfone milipore filter, is characterized in that: raw material quality number is respectively polyether sulfone 10-25 part, polyvinyl alcohol 0.05-2 part, organic solvent 60-85 part, pore-foaming agent 2-15 part, crosslinking agent A0.05-2 part, crosslinking agent B 0.05-2 part.
Described material quality number is respectively polyether sulfone 15 parts, polyvinyl alcohol 1 part, organic solvent 70 parts, pore-foaming agent 11 parts, crosslinking agent A1.5 part, crosslinking agent B 1.5 parts.
Described organic solvent be 1-METHYLPYRROLIDONE (NMP), DMF (DMF), DMA (DMAC), dimethyl sulfoxide (DMSO) (DMSO) any one.
Described pore-foaming agent is PEG400 (PEG400), PEG600 (Macrogol 600), PEG1000 (cetomacrogol 1000), PEG2000 (Macrogol 2000), PEG6000 (Macrogol 6000), PEG10000 (PEG20000), PVP
k15(polyvinylpyrrolidone K15), PVP
k30(PVP K30), PVP
k40(polyvinylpyrrolidone k40), PVP
k60(polyvinylpyrrolidone k60), PVP
k80(polyvinylpyrrolidone k80), PVP
k90any one of (PVP K90) and lithium chloride (LiCl).
Described crosslinking agent A be citric acid, oxalic acid, malic acid, tartaric any one.
Described crosslinking agent B is glutaraldehyde.
A preparation method for 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 after adopting agitator to stir, add the pore-foaming agent of above-mentioned mass parts, and continue to adopt agitator to be uniformly mixed, after leaving standstill 12-24h, vacuum defoamation is carried out to mixed liquor, obtains clear transparent solutions.
(2) by step 1) clear transparent solutions that obtains is placed on non-woven fabrics and carries out knifing, then be placed on reverse-osmosis treated 10-20h in 60-80 DEG C of water.
(3) by step 2) milipore filter that obtains just finished product be placed in the sulfuric acid that concentration is 1%, add crosslinking agent A and the crosslinking agent B of above-mentioned mass parts successively wherein, and then by cross-linking reaction, crosslinking agent A and crosslinking agent B are grafted to the surface of the first finished product of milipore filter, obtain milipore filter semi-finished product.
(4) by step 3) after the milipore filter semi-finished product that obtain are placed in water reverse-osmosis treated 1-5 time of 50-70 DEG C, each anti-penetration wastewater disposal 3-7min, can obtain milipore filter.
Described agitator stirs as mechanical agitation, and its mixing speed is 80-100r/min.
The vacuum of described vacuum defoamation is 0.02-0.08MPa.
The amount of 1% described sulfuric acid is that first finished product is (1-2.3) according to mass ratio with milipore filter: (0.9-1.3); The time of described vacuum defoamation is 10-30min.
Above-mentioned polyether sulfone used is the thermoplastic macromolecule material of a kind excellent combination property; It has excellent heat resistance, physical and mechanical properties, insulating properties etc., particularly has can at high temperature to use continuously and still can the outstanding advantages such as retention is stable in temperature environment jumpy.
Polyvinyl alcohol described above is organic compound, white plates, cotton-shaped or pulverulent solids, tasteless, water-soluble, be slightly soluble in dimethyl sulfoxide (DMSO).
Non-woven fabrics described above, refers to non-weaving cloth, or is adhesive-bonded fabric.Be a kind ofly do not need to spin cotton and weave cloth and the fabric that formed, just textile staple or long filament carried out orientation or support row at random, forming fibre net structure, then adopt machinery, the method such as hot sticky or chemical reinforces and form.
Knifing described above coats layer of substance at certain base material surface exactly.
Cross-linking reaction described above, refers to that the linear polymeric with certain degree of polymerization carries out cross-linking reaction under the crosslinked action of crosslinking agent, linear polymeric is interconnected to form have the network structure macromolecule of certain crosslink density.
Counter-infiltration described above, refers to the reverse travel motion of the one of infiltration, be a kind of under pressure-driven by means of the separation method that the solute in solution and solvent separate by the selective retention effect of pellicle, its aperture is greatly about 5 ~ 10A.It has been widely used in the purification of various liquid with concentrated, wherein the most general application example is in water treatment technology, can by Impurity removals such as the inorganic ions in former water, bacterium, virus, organic matter and colloids with reverse osmosis technology, to obtain high-quality pure water.
Compared with prior art, tool of the present invention has the following advantages and technique effect:
1. by polyether sulfone and polyvinyl alcohol are dissolved in organic solvent successively, and after adopting agitator to stir, add pore-foaming agent, and by carrying out vacuum defoamation to mixed liquor, obtain clear transparent solutions, this clear transparent solutions is placed on non-woven fabrics and carries out knifing, and under the effect of sulfuric acid, crosslinking agent A and crosslinking agent B are carried out cross-linking reaction, makes the film preparing out have the features such as good durability, stable performance.
2. by each raw material quality number dosage with produce supermembrane flow process and carry out research and discussion, draw the supermembrane that can meet many performance requirements, overcome the properties removing to meet milipore filter from single aspect, decrease raw-material waste, reduce the use cost of membrane technology, improve the serviceability of membrane material, the perfect further technology in masking field.
3. by pore-foaming agent being added in the organic solvent of polyether sulfone and polyvinyl alcohol dissolution, mixed solution is diffuseed to form rapidly poroid, and then improve the situation of scraping mixed solution skewness on non-woven fabrics in membrane process, and be that 1% sulfuric acid carries out cross-linking reaction by adding mass percent, crosslinking agent A and crosslinking agent B are grafted to ultrafiltration membrane surface, thus obtain there is the milipore filter that stain resistance is strong, hydrophilic layer not easily runs off.
Detailed description of the invention
Below by embodiment, the present invention is specifically described.What be necessary to herein means out is that the present embodiment is only for being described further invention and understanding; it is not limiting the scope of the invention; if improvement and adjustment that those skilled in the art makes some non-outstanding essential characteristics and non-significant progress according to the invention described above content to the present invention, still belong to scope.
Embodiment 1
A kind of hydrophilic polyethersulfone milipore filter, its raw material is polyether sulfone 15kg, polyvinyl alcohol 0.05kg, dimethyl sulfoxide (DMSO) (DMSO) for 82.95kg, PEG400 (PEG400) be 2kg, citric acid is 0.05kg, and glutaraldehyde is 0.05kg.
Its concrete 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 after adopting agitator to stir, add the pore-foaming agent of above-mentioned mass parts, and continue to adopt agitator to be uniformly mixed, after leaving standstill 12h, vacuum defoamation is carried out to mixed liquor, obtains clear transparent solutions.
(2) by step 1) clear transparent solutions that obtains is placed on non-woven fabrics and carries out knifing, then be placed on reverse-osmosis treated 15h in 60 DEG C of water.
(3) by step 2) milipore filter that obtains just finished product be placed in the sulfuric acid that concentration is 1%, add citric acid and the glutaraldehyde of above-mentioned mass parts successively wherein, and then by cross-linking reaction, citric acid and glutaraldehyde are grafted to the surface of the first finished product of milipore filter, obtain milipore filter semi-finished product.
(4) by step 3) after the milipore filter semi-finished product that obtain are placed in the water reverse-osmosis treated 5 times of 50 DEG C, each anti-penetration wastewater disposal 3min, can obtain milipore filter.
Agitator wherein stirs as mechanical agitation, and its mixing speed is 80r/min; The vacuum of vacuum defoamation is 0.02MPa; The amount of the concentrated sulfuric acid is that first finished product is 1:0.9 according to mass ratio with milipore filter; The time of vacuum defoamation is 10min.
By detecting the performance of the milipore filter obtained: the performance that it has resistance tocrocking, hydrophilic layer not easily runs off.
Embodiment 2
A kind of hydrophilic polyethersulfone milipore filter, on the basis of embodiment 1, other preparation method's steps are with embodiment 1, its raw material is polyether sulfone 20kg, polyvinyl alcohol 0.05kg, dimethyl sulfoxide (DMSO) (DMSO) for 77.95kg, PEG400 (PEG400) be 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's steps are with embodiment 1, its raw material is polyether sulfone 18kg, polyvinyl alcohol 0.05kg, dimethyl sulfoxide (DMSO) (DMSO) for 79.95kg, PEG400 (PEG400) be 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's steps are with embodiment 1, its raw material is polyether sulfone 18kg, polyvinyl alcohol 2kg, dimethyl sulfoxide (DMSO) (DMSO) for 78kg, PEG400 (PEG400) be 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's steps are with embodiment 1, its raw material is polyether sulfone 15kg, polyvinyl alcohol 2kg, dimethyl sulfoxide (DMSO) (DMSO) for 81kg, PEG400 (PEG400) be 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's steps are with embodiment 1, its raw material is polyether sulfone 18kg, polyvinyl alcohol 2kg, dimethyl sulfoxide (DMSO) (DMSO) for 80kg, PEG400 (PEG400) be 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's steps are with embodiment 1, its raw material is polyether sulfone 20kg, polyvinyl alcohol 1kg, dimethyl sulfoxide (DMSO) (DMSO) for 82kg, PEG400 (PEG400) be 11kg, citric acid is 1kg, and glutaraldehyde is 1kg.
Test example:
Index after the properties had milipore filter of the present invention below by following test example and properties combine detects, specifically:
Experimental example 1 hydrophilicity experiment
1.1 test material
The uncovered water tumbler that ten sizes are identical, clear water, the milipore filter of the embodiment of the present invention 1, " method for preparing hydrophilic low catching molecular composite ultrafiltering membrane " of documents CN200710037396.7 obtained product composite hyperfiltration membrane is as test control group.Be denoted as A, B, C, D, E five groups, carry out check experiment.
1.2 test method
Get ten water tumblers (500ml), two one group, be divided into five groups, often organize a milipore filter being used for placing the embodiment of the present invention 1 in water tumbler and be numbered 1, another placement is numbered 2 by the composite hyperfiltration membrane that " method for preparing hydrophilic low catching molecular composite ultrafiltering membrane " of documents CN200710037396.7 is obtained.And be respectively 40g for the weight of two kinds of milipore filters of testing, for the surface area (cm of two kinds of milipore filters tested
2) be all 5*5=25cm
2, consistency of thickness.Comparatively be placed in ten water tumblers by the milipore filter obtained by specification, in each water tumbler, the clear water of 250ml carries out test in 5 minutes.
1.3 experimental result
The milipore filter taken out in each water tumbler is weighed, and its weight is respectively shown in table 1:
Hydrophilic test (the unit: g) of table 1
As seen from the above table, the hydrophily of the hydrophilic polyethersulfone milipore filter that the present embodiment 1 is made is better, and hydrophilicity is evenly distributed, better than existing hydrophilic low catching molecular composite ultrafiltering membrane effect, has significant effect.
Strong and the hydrophilic layer of experimental example 2 stain resistance not easily runs off and tests
2.1 experiment material
Sanitary sewage (filtering block larger material) is some, the milipore filter of the embodiment of the present invention 1, the perforated membrane that " the preparing the method for Hydrophilized porous membrane " of documents CN201010210573.9 makes as test control group, the identical water pipe that two length is 0.5m, bore is 10cm.Two longer thin wires.
2.2 test method
Above-mentioned two kinds of supermembrane materials are divided into surface area (cm respectively
2) be 15*15=225cm
2, cover one end of water pipe with milipore filter, fixed filter membrane with thin wire, make to form an entirety between milipore filter and water pipe, obtain a membrane filter, the one end having film is the low side of filter, does not have one end of film to be top.According to method recited above, two kinds of filter membranes are separately fixed on two water pipes, obtain two membrane filters.Being placed on respectively by two of gained filters becomes the length and width at 15 ° of angles to be respectively above 0.6m, 0.5m plank with surface water plane, and the top of two filter membrane devices upward, and bottom is down, and placed side by side.Then by some sewage continuously, introduce in two filters with the identical water yield, duration is 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 describes its film properties and stablizes; And very limpid through the sewage of this filter, there is significant effect compared with the perforated membrane made with " the preparing the method for Hydrophilized porous membrane " of existing file CN201010210573.9.
It is important to point out at this; above embodiment and test example are only limitted to do further explaination to the technique effect of technical scheme of the present invention; can not be interpreted as and further restriction is done to technical scheme of the present invention; the substantive distinguishing features of the non-protruding that those skilled in the art make on this basis and the improvement of marked improvement, still belong to protection category of the present invention.