CN103990386A - Production method of micro-porous filter membrane with positive charges - Google Patents
Production method of micro-porous filter membrane with positive charges Download PDFInfo
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- CN103990386A CN103990386A CN201410241749.5A CN201410241749A CN103990386A CN 103990386 A CN103990386 A CN 103990386A CN 201410241749 A CN201410241749 A CN 201410241749A CN 103990386 A CN103990386 A CN 103990386A
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- 239000000203 mixture Substances 0.000 claims description 21
- 229920006393 polyether sulfone Polymers 0.000 claims description 20
- 239000004695 Polyether sulfone Substances 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 14
- 229920002521 macromolecule Polymers 0.000 claims description 14
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 11
- 150000001412 amines Chemical class 0.000 claims description 11
- 239000004088 foaming agent Substances 0.000 claims description 9
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- 229920002292 Nylon 6 Polymers 0.000 claims description 8
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 239000012633 leachable Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 229920002678 cellulose Polymers 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001471 micro-filtration Methods 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 238000001035 drying Methods 0.000 abstract description 3
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- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 10
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- 239000011324 bead Substances 0.000 description 8
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- 239000000975 dye Substances 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000000129 anionic group Chemical group 0.000 description 3
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Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention provides a production method of a micro-porous filter membrane with positive charges. The production method comprises the following steps: dissolving an uncharged neutral polymer solid material and additives in an organic solvent; adding a pore-forming agent, and poly-functional monomers and a poly-functional cross-linking agent which can form polymer cross-linking bonds with the positive charges, mixing uniformly, and stirring to dissolve so as to prepare a membrane casting solution; removing air bubbles from the solution by a vacuum or standing method; uniformly coating the membrane casting solution on a glass plate in a scratching manner; placing the glass plate into a molding chamber with water vapor; blowing water vapor into the molding chamber to form a primary filter membrane; stripping the primary filter membrane from the glass plate; immersing water soluble substances of the primary filter membrane in pure water; performing high molecular reaction at the temperature of 70 to 90 DEG C and drying to obtain the micro-porous filter membrane with positive charges. According to the production method, the membrane casting solution is prepared by functional raw materials with the positive charges and a substrate for preparing the micro-porous filter membrane; compared with the prior art, post-processing steps are avoided; the manufacturing method is simplified; moreover, the firmness of the positive charges of the prepared micro-porous filter membrane is high.
Description
Technical field
The present invention relates to a kind of semi permeable hydrophilic miillpore filter, particularly aperture and be encompassed in the miillpore filter between 0.01 micron to 10 microns.
Background technology
Miillpore filter is to utilize macromolecule chemical material, and pore additive spreads upon on supporting layer and is made after specially treated.In application of membrane separation technology, miillpore filter is a kind of film kind that range of application is the widest, use simple, quick, be widely used in the various fields such as scientific research, food inspection, chemical industry, nanometer technology, the energy and environmental protection.Common miillpore filter Base Material used is solubility engineering plastics, comprises polysulfones, polyether sulfone, polysulfones/polyether sulfone mixture, nylon 6, nylon 6/6, nylon 4/6, polyvinylidene fluoride, cellulose mixture etc.For example celluloid miillpore filter is that use celluloid is base material, add appropriate cellulose acetate, acetone, n-butanol, ethanol, etc. make, hydrophilic, there is non-toxic sanitary, it is a kind of porous membrane filtration material, the micropore of the more even penetrability of pore-size distribution, microporosity is up to 80% absolute aperture.Be mainly used in the filtration of aqueous solution, therefore also claim water system film.
In filtration application, the function of miillpore filter is to remove the solid impurity being present in gas or liquid, for example: bacterium, microorganism or fine particle etc.Miillpore filter developed and commercial production for many years, its filtration mechanism is returned to divide two classes into substantially:
The first kind is to utilize the inner pore size of filter membrane and the correlation of filtering impurities granular size in fluid, to reach its filtering function.In brief, be to utilize smaller aperture contained in filter membrane to intercept passing through of larger particles impurity, to complete the object of impurity screening.In other words, if impurity particle is larger than filter membrane aperture, can by filter membrane hole intercept in outside.Otherwise impurity particle can penetrate filter membrane hole and cannot reach the filter effect that expection is removed.
Equations of The Second Kind is utilize electric charge and the carried charge of filter membrane pore surface and filter the correlation between impurities particle surface static in fluid.Generally speaking, filter under environment in neutrality, most of interior impurities particle of fluid that filters is all with micro-negative electrical charge, if miillpore filter pore surface is with positive charge, utilize the positive negative of electric charge to inhale principle, even less than filter membrane hole with the impurity particle size of micro-negative electrical charge, also can be adsorbed by the filter membrane with positive charge, flow out and can not penetrate filter membrane, saturated until filter membrane pore surface positive charge is completely exhausted.
Require more and more high in pharmacy and microelectronic industry filtering accuracy in recent years, the neutral filter membrane of tradition small-bore, for example 0.1 micron of even also rising rapidly of demand of 0.03 micron, but the neutral miillpore filter of small-bore has its congenital shortcoming in its filtration application: for example, when filtration, must use higher filtration pressure difference, increase the difficulty of operation.In addition, use the filter membrane of smaller aperture due, discharge and flux are inevitable not high, can not meet filtration user and require expectation of high flow capacity etc.Based on this, invent a kind of filtered water flow and flux is high and still have the filter membrane of high impurity rejection, become pursuing a goal of filter membrane circle.
The applicant's the patent No. is the preparation method that 201010298873.7 formerly patent has proposed a kind of positive charge microfiltration membrane, the method using is the microporous membrane surface neutral (not charged), monomer crosslinked dose of cover tape positive charge, catalyst etc., through high-temperature macromolecule chemical reaction, form positively charged miillpore filter, that is to say that modification becomes positively charged miillpore filter the miillpore filter of neutral (not charged).This patent exists technique loaded down with trivial details, the problem that positive charge firmness is low.
Summary of the invention
The object of this invention is to provide a kind of production method of positively charged miillpore filter, to solve the loaded down with trivial details puzzlement of existing positively charged miillpore filter preparation method technique, and prepared positively charged miillpore filter, there is the problem that positive charge firmness is low.
For achieving the above object, the present invention is by the following technical solutions:
A production method for positively charged miillpore filter, comprises the following steps:
A, uncharged neutral polymeric solid material and additive are dissolved in organic solvent, add pore-foaming agent and can form polyfunctional monomer and the multi-group crosslink agent of the crosslinked bond of positively charged macromolecule, evenly mix, stirring and dissolving is mixed with casting solution;
B, casting solution that step a is prepared, after homogeneous phase solution forms, use vavuum pump or settled process to get rid of in solution because stirring the bubble producing;
C, utilize scraper by even casting solution blade coating on glass plate, insert the forming room of containing steam, be blown into steam to form nascent filter membrane, then the filter membrane of moulding is peeled off from glass plate;
D, immerse the water leachable 2 hours that soaks nascent filter membrane in pure water, finally by temperature 70-90 DEG C carry out polymer chemistry reaction and dry after, obtain positively charged miillpore filter.
In step a, the mass percent of the raw material of preparation casting solution is:
Uncharged neutral polymeric solid material 10 ~ 20%;
Pore-foaming agent 0 ~ 25%, but do not comprise 0;
Can form the polyfunctional monomer 0.1 ~ 20% of positively charged crosslinked bond;
Multi-group crosslink agent 0.1 ~ 20%;
Additive 0.1 ~ 10%;
All the other are organic solvent.
The described polyfunctional monomer that can form positively charged crosslinked bond is polyfunctional group glycidol ether, and multi-group crosslink agent is polyfunctional group macromolecule amine.
Preferably, described polyfunctional group glycidol ether is BDO glycidol ether, and its structural formula is:
；
Or the chemical substance similar to BDO glycidol ether chemistry character.
Preferably, described polyfunctional group macromolecule amine is polymine, and its chemical structural formula is: (CH
2cH
2nR)
n, wherein, R is hydrogen atom or successional macromolecule amine key, n=900 ~ 1400;
Or the organic amine of TEPA, five ethene hexamines or other similar structures.
Described uncharged neutral polymeric solid material is the one in polysulfones, polyether sulfone, polysulfones/polyether sulfone mixture, nylon 6, nylon 6/6, nylon 4/6, polyvinylidene fluoride, cellulose mixture.
Described pore-foaming agent is the mixture of one or more arbitrary proportions in polyethylene glycol, acetone, ethanol.
Described organic solvent is the mixture of one or more arbitrary proportions in dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), dioxane.
Described additive is polyvinylpyrrolidone or the chemical substance similar to polyvinylpyrrolidone chemical property.
The pore size scope of described miillpore filter is 0.01 micron to 10 microns.
In step c, the step that forms nascent filter membrane is: the thickness raw material on glass plate is positioned in the forming room of 60 ~ 70% relative humidity, and accepts steam and brush, until thickness raw material bleaches; In steps d, nascent filter membrane is positioned in baking oven through temperature 70-90 DEG C high temperature and carries out polymer chemistry reaction and to till dry.
Method of the present invention is forming positively charged cross-linked polymer monomer and crosslinking agent, insert in the casting solution of miillpore filter, casting solution is accepted to steam and brush to form nascent filter membrane, remove solvent through cleaning process again, react to form finally by high-temperature macromolecule cross-linking chemistry and include positively charged crosslinked polymeric miillpore filter.
The invention has the beneficial effects as follows: in the production method of positively charged miillpore filter of the present invention, directly be mixed with casting solution with the functional raw material of positive charge with the base material of preparing miillpore filter, than prior art without post-processing step, preparation method is more simplified, and uses the firmness of positive charge of the miillpore filter that makes of the present invention high.Technique of the present invention is simple, easy and simple to handle, and the positively charged miillpore filter of hydrophily of producing, has good discharge and filtration flux.Compared with the same apertures miillpore filter of crossing without PROCESS FOR TREATMENT of the present invention, this positively charged miillpore filter can be held back smaller sized particles impurity.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention will be further described
A production method for positively charged miillpore filter, comprises the following steps:
Step a, uncharged neutral polymeric solid material and additive are dissolved in organic solvent, add pore-foaming agent and can form polyfunctional monomer and the multi-group crosslink agent of the crosslinked bond of positively charged macromolecule, evenly mix, stirring and dissolving is mixed with casting solution;
The mass percent of the raw material of preparation casting solution is:
Uncharged neutral polymeric solid material 10 ~ 20%;
Pore-foaming agent 0 ~ 25%, but do not comprise 0;
Can form the polyfunctional monomer 0.1 ~ 20% of positively charged crosslinked bond;
Multi-group crosslink agent 0.1 ~ 20%;
Additive 0.1 ~ 10%;
All the other are organic solvent.
The polyfunctional monomer that can form positively charged crosslinked bond is polyfunctional group glycidol ether, preferably BDO glycidol ether, and its structural formula is:
；
Or the chemical substance similar to BDO glycidol ether chemistry character;
Multi-group crosslink agent is polyfunctional group macromolecule amine, preferably polyethylene imines, and its chemical structural formula is: (CH
2cH
2nR)
n, wherein, R is hydrogen atom or successional macromolecule amine key, n=900 ~ 1400;
Or the organic amine of TEPA, five ethene hexamines or other similar structures;
One in the preferred polysulfones of uncharged neutral polymeric solid material, polyether sulfone, polysulfones/polyether sulfone mixture, nylon 6, nylon 6/6, nylon 4/6, polyvinylidene fluoride, cellulose mixture;
The mixture of one or more arbitrary proportions in the preferred polyethylene glycol of pore-foaming agent, acetone, ethanol;
The mixture of one or more arbitrary proportions in the preferred dimethyl formamide of organic solvent, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), dioxane;
Additive preferably polyethylene pyrrolidones or the chemical substance similar to polyvinylpyrrolidone chemical property, the effect of additive is to make the filter membrane of preparing have hydrophily.
Step b, casting solution that step a is prepared, after homogeneous phase solution forms, use vavuum pump or settled process to get rid of in solution because stirring the bubble producing.
Step c, utilize scraper by even casting solution blade coating on glass plate, insert the forming room of containing steam, be blown into steam to form nascent filter membrane, thickness raw material on glass plate is positioned in the forming room of 60 ~ 70% relative humidity, and accept steam and brush, until thickness raw material bleaches, then the filter membrane of moulding is peeled off from glass plate;
Steps d, immerse the water leachable that soaks nascent filter membrane in pure water more than 2 hours, finally by temperature 70-90 DEG C carry out polymer chemistry reaction and dry after, obtain positively charged miillpore filter.
The pore size scope of above-mentioned miillpore filter is 0.01 micron to 10 microns.
Below in conjunction with specific embodiment and comparative example, the present invention will be further described.
Term definition:
Steam bubble point: the test of steam bubble point is to measure the conventional easy means of the one in miillpore filter aperture.First that filter membrane is fully wetting with suitable liquid when test.As filter membrane be hydrophily conventional pure water is wetting, though as filter membrane be that hydrophobicity or hydrophily aperture are less than 0.1 micron, conventional ethanol or isopropyl alcohol are wetting.After filter membrane is wetting, use compressed air that air is clamp-oned in filter membrane by the hole of suitable liquid lock, in the time that air pressure reaches a certain numerical value, the liquid in hole can be squeezed out at once.Now liquid can be squeezed to the i.e. steam bubble of the filter membrane point for this reason of the minimum pressure of draining.In principle, filter membrane aperture is larger, and corresponding steam bubble point is lower.In miillpore filter circle, often use bubble point to define the pore size of filter membrane.
Discharge: under quantitative pure water volume, the filter membrane of unit are, at specified pressure and temperature, filter the required time of quantitative pure water.Substantially, millipore water flow is higher, the quantitative pure water required time that filters fewer, shown filter membrane percent opening is larger, this term is also by filter membrane circle is commonly used.
Anionic dye adsoptivity: positively charged filter membrane will adsorpting anion dyestuff, its adsoptivity can be as the carried charge of estimating positive charge filter membrane.
Filter membrane extract total amount: filter membrane extract total amount is that filter membrane is immersed in and is boiled continuously the weight of losing after 1 hour in pure water.
Latex beads ball rejection: latex beads ball rejection is a kind of quantitative measurment of measuring filtering with microporous membrane trapped particles impurity.When operation, use the monodisperse polystyrene latex beads ball of known diameter specification, be suspended in the aqueous solution, under negative pressure condition, pass through the miillpore filter sample of known pore size, the quantitative filtering liquid that its downstream is collected, under specific wavelength of light, can measure the latex beads ball rejection of filter membrane through ultraviolet/visible light spectral instrument.
Below in conjunction with specific embodiment, the present invention will be further described.
comparative example 1
Prepare the neutral neutral polyethersulfone millipore filter of 0.1 micron pore size
Polyether sulfone, dimethyl formamide, polyethylene glycol, polyvinylpyrrolidone are according to the ratio blend of weight ratio 15:16:67.5:1.5 stirring.After homogeneous phase solution forms, use vavuum pump or static method to get rid of in solution because stirring the bubble producing.Then utilize scraper evenly to scrape raw material that 0.5 millimeter is thick on glass plate.Thickness raw material on glass plate is positioned in the forming room of 70% relative humidity, and accept steam and brush, until thickness raw material bleaches, then immerse the water leachable 2 hours that soaks nascent filter membrane in pure water, finally nascent filter membrane is positioned in baking oven under temperature 70 C 30 minutes until dry.
With the produced filter membrane of this method, there is hydrophily and can be at once by the characteristic of water-wet.With its ethanol vapor bubble point of the produced filter membrane of this method be 3.4 kg/cm, under 24 inch of mercury pressure, discharge is 96 seconds/100 ml pure water/9.62 square centimeter filter areas.
comparative example 2
Prepare 0.1 micron of positively charged polyethersulfone millipore filter of hydrophily
Polymine-3-is chloro-1, and 2-expoxy propane, quaternary ammoniated mixed poly dimethyl amine-3-are chloro-1, and 2-expoxy propane, potassium hydroxide, tetrabutylammonium bromine, pure water are mixed and stirred mutually with the ratio of 2:2:2:1:93 according to weight ratio, to prepare positive charge treatment fluid.Then 0.1 micron of hydrophilic polyethersulfone millipore filter prepared in comparative example 1, be slowly immersed in positive charge treatment fluid and guarantee that overall filter membrane is without dry blind spot., take out filter membrane and strike off surface unnecessary positive charge treatment fluid, carry out at once 140 DEG C of high-temperature bakings and process 15 minutes thereafter.After high temperature processing step, use the deionization pure water of 90 DEG C to carry out at once filter membrane cleaning 20 minutes, last, at 70 DEG C of temperature, carry out final drying 15 to 20 minutes.
With its steam bubble point of the produced filter membrane of this method be 3.5 kg/cm, under 24 inch of mercury pressure, discharge is 101 seconds/100 ml pure water/9.62 square centimeter filter areas.
embodiment 1
Prepare the positively charged polyethersulfone millipore filter of 0.1 micron pore size
Polyether sulfone, dimethyl formamide, polyethylene glycol, polyvinylpyrrolidone, polymine, 1,4-butanediol glycidol ether is according to the ratio blend of weight ratio 18:34:10:10:20:8 stirring, after homogeneous phase solution forms, use vavuum pump or static method to get rid of in solution because stirring the bubble producing.Then utilize scraper evenly to scrape raw material that 0.5 millimeter is thick on glass plate.Thickness raw material on glass plate is positioned in the forming room of 70% relative humidity, and accept steam and brush, until thickness raw material bleaches, then immerse in pure water the water leachable 2 hours that soaks nascent filter membrane, finally nascent filter membrane be positioned in baking oven 90 DEG C of temperature carry out polymer chemistry reaction and dry after, obtain positively charged miillpore filter.
It is wetting at once that the filter membrane that this embodiment produces is met pure water, belongs to hydrophilic filter membrane, and its ethanol vapor bubble point is 3.6 kg/cm, and under 24 inch of mercury pressure, discharge is 108 seconds/100 ml pure water/9.62 square centimeter filter areas.
embodiment 2
Prepare the positively charged polyethersulfone millipore filter of 0.2 micron pore size
Polyether sulfone, dimethylacetylamide, polyethylene glycol, polyvinylpyrrolidone, TEPA, 1,4-butanediol glycidol ether is according to the ratio blend of weight ratio 15:37:25:3:10:10 stirring, after homogeneous phase solution forms, use vavuum pump or static method to get rid of in solution because stirring the bubble producing.Then utilize scraper evenly to scrape raw material that 0.5 millimeter is thick on glass plate.Thickness raw material on glass plate is positioned in the forming room of 70% relative humidity, and accept steam and brush, until thickness raw material bleaches, then immerse in pure water the water leachable 2 hours that soaks nascent filter membrane, finally nascent filter membrane be positioned in baking oven 90 DEG C of temperature carry out polymer chemistry reaction and dry after, obtain positively charged miillpore filter.
It is wetting at once that the filter membrane that this embodiment produces is met pure water, belongs to hydrophilic filter membrane, and its steam bubble point is 3.7 kg/cm, and under 24 inch of mercury pressure, discharge is 30 seconds/100 ml pure water/9.62 square centimeter filter areas.
embodiment 3
Prepare the positively charged polyethersulfone millipore filter of 5 micron pore size
Polyether sulfone, 1-METHYLPYRROLIDONE, polyethylene glycol, polyvinylpyrrolidone, five ethene hexamines, 1,4-butanediol glycidol ether is according to the ratio blend of weight ratio 12:57:5:1:5:20 stirring, after homogeneous phase solution forms, use vavuum pump or static method to get rid of in solution because stirring the bubble producing.Then utilize scraper evenly to scrape raw material that 0.6 millimeter is thick on glass plate.Thickness raw material on glass plate is positioned in the forming room of 60% relative humidity, and accept steam and brush, until thickness raw material bleaches, then immerse in pure water the water leachable 2 hours that soaks nascent filter membrane, finally nascent filter membrane be positioned in baking oven 80 DEG C of temperature carry out polymer chemistry reaction and dry after, obtain positively charged miillpore filter.
It is wetting at once that the filter membrane that this embodiment produces is met pure water, belongs to hydrophilic filter membrane, and its steam bubble point is 0.5 kg/cm, and under 3 inches of mmhg pressures, discharge is 26 seconds/250 ml pure water/9.62 square centimeter filter areas.
test example 1
The positive charge adsorbance of filter membrane is measured
The filter membrane that comparative example 1 ~ 2, embodiment 1 ~ 3 are produced is tested respectively as follows:
Use the metanil yellow aqueous solution of 10ppm concentration as adsorption liquid, under 0.8 kg/cm pressure, flow through thickness between 0.09 to 0.12 millimeter and diameter is the filter membrane disk sample of 47 millimeters, till its saturated extent of adsorption starts to become micro-Huang with the collected filtered fluid in visual its downstream.The visual error of its saturated terminal is at ± 10 milliliters of metanil yellow solution.
In the time of 1 milliliter of every filtration, depending on the color of diaphragm, and detect the color in filtered fluid downstream, in the time of the visible yellow color solution of filtered fluid downstream, the anionic dye of testing diaphragm reaches saturation degree.
Test result is as table 1
Table 1
Shown that by above-mentioned data positively charged filter membrane of the present invention, than the poly (ether sulfone) film of 0.1 micron pore size that is the positively charged neutrality in comparative example 1, adsorbs 5 times of above anionic dyes more.
test example 2
The positive charge absorption firmness of filter membrane is measured
The filter membrane that comparative example 2, embodiment 1 ~ 3 are produced is tested respectively as follows:
Filter membrane is immersed in pure water and is boiled 36 hours, take out filter membrane, use normal temperature pure water to clean at once 30 minutes, last, at 70 DEG C of temperature, carry out final drying 15 to 20 minutes, and carry out the test in test example 1.
Test result is as table 2
Table 2
Shown by above-mentioned data, the positively charged miillpore filter of comparative example 2 is after hot water treatment, and electrified degree obviously declines.And positively charged miillpore filter of the present invention, after the same terms hot water treatment, electrified degree is substantially constant.This result demonstration, according to the prepared positively charged miillpore filter of the present invention, its positive charge firmness is high.
test example 3
latex beads ball rejection is measured
Use is suspended in pure water, 0.198 micron diameter monodisperse polystyrene latex beads ball of 20 ppm concentration, as test fluid, under the pressure of 0.8 kg/cm, get the test fluid of 10 milliliters, flow through thickness between 0.09 to 0.12 millimeter and the filter membrane disk sample of 47 millimeters of diameters, collect filtrate.This filtrate and former test fluid are done quantitative analysis through UV/visible spectrophotometer device, can record the latex beads ball rejection of filter membrane disk sample.
Test result is as table 3
Table 3
Shown that by above-mentioned data positively charged filter membrane of the present invention, than the polyethersulfone millipore filter that is neutrality 0.1 micron pore size in comparative example 1, adsorbs the latex beads ball of 3 times of 0.198 above micron diameters more.
Claims (10)
1. a production method for positively charged miillpore filter, is characterized in that: comprise the following steps:
A, uncharged neutral polymeric solid material and additive are dissolved in organic solvent, add pore-foaming agent and can form polyfunctional monomer and the multi-group crosslink agent of the crosslinked bond of positively charged macromolecule, evenly mix, stirring and dissolving is mixed with casting solution;
B, casting solution that step a is prepared, after homogeneous phase solution forms, use vavuum pump or settled process to get rid of in solution because stirring the bubble producing;
C, utilize scraper by even casting solution blade coating on glass plate, insert the forming room of containing steam, be blown into steam to form nascent filter membrane, then the filter membrane of moulding is peeled off from glass plate;
D, immerse the water leachable 2 hours that soaks nascent filter membrane in pure water, finally by temperature 70-90 DEG C carry out polymer chemistry reaction and dry after, obtain positively charged miillpore filter.
2. the production method of positively charged miillpore filter as claimed in claim 1, is characterized in that: in step a, the mass percent of the raw material of preparation casting solution is:
Uncharged neutral polymeric solid material 10 ~ 20%;
Pore-foaming agent 0 ~ 25%, but do not comprise 0;
Can form the polyfunctional monomer 0.1 ~ 20% of positively charged crosslinked bond;
Multi-group crosslink agent 0.1 ~ 20%;
Additive 0.1 ~ 10%;
All the other are organic solvent.
3. the production method of positively charged miillpore filter as claimed in claim 1 or 2, is characterized in that: the described polyfunctional monomer that can form positively charged crosslinked bond is polyfunctional group glycidol ether, and multi-group crosslink agent is polyfunctional group macromolecule amine.
4. the production method of positively charged miillpore filter as claimed in claim 3, is characterized in that: described polyfunctional group glycidol ether is BDO glycidol ether, and its structural formula is:
；
Or the chemical substance similar to BDO glycidol ether chemistry character.
5. the production method of positively charged miillpore filter as claimed in claim 3, is characterized in that: described polyfunctional group macromolecule amine is polymine, and its chemical structural formula is: (CH
2cH
2nR)
n, wherein, R is hydrogen atom or successional macromolecule amine key, n=900 ~ 1400;
Or the organic amine of TEPA, five ethene hexamines or other similar structures.
6. the production method of positively charged miillpore filter as claimed in claim 1 or 2, is characterized in that: described uncharged neutral polymeric solid material is the one in polysulfones, polyether sulfone, polysulfones/polyether sulfone mixture, nylon 6, nylon 6/6, nylon 4/6, polyvinylidene fluoride, cellulose mixture.
7. the production method of positive charge microfiltration membrane as claimed in claim 1 or 2, is characterized in that: described pore-foaming agent is the mixture of one or more arbitrary proportions in polyethylene glycol, acetone, ethanol.
8. the production method of positive charge microfiltration membrane as claimed in claim 1 or 2, is characterized in that: described organic solvent is the mixture of one or more arbitrary proportions in dimethyl formamide, dimethylacetylamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), dioxane; Described additive is polyvinylpyrrolidone or the chemical substance similar to polyvinylpyrrolidone chemical property.
9. the production method of positively charged miillpore filter as claimed in claim 1, is characterized in that: the pore size scope of described miillpore filter is 0.01 micron to 10 microns.
10. the production method of positively charged miillpore filter as claimed in claim 1, it is characterized in that: in step c, the step that forms nascent filter membrane is: the thickness raw material on glass plate is positioned in the forming room of 60 ~ 70% relative humidity, and accepts steam and brush, until thickness raw material bleaches; In steps d, nascent filter membrane is positioned in baking oven through temperature 70-90 DEG C high temperature and carries out polymer chemistry reaction and to till dry.
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|---|---|---|---|---|
| CN109776831A (en) * | 2019-03-20 | 2019-05-21 | 福州大学 | A kind of fast preparation method of self-supporting hydroxide film and metal organic framework film |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03186325A (en) * | 1989-11-30 | 1991-08-14 | Millipore Corp | Porous membrane formed of interstitial network of polymer and having hydrophilic surface |
| US5277812A (en) * | 1993-02-12 | 1994-01-11 | Gelman Sciences Inc. | Inter-penetrating network charge modified microporous membrane |
| CN101274227A (en) * | 2007-03-28 | 2008-10-01 | 宁波大学 | A kind of preparation method of polymer microfiltration membrane |
| CN102008898A (en) * | 2010-10-08 | 2011-04-13 | 亚美滤膜（南通）有限公司 | Method for preparing positive charge microfiltration membrane |
| CN102580572A (en) * | 2012-03-06 | 2012-07-18 | 中国科学技术大学 | Anion-exchange membrane and preparation method thereof |
| CN103446899A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof |
-
2014
- 2014-06-03 CN CN201410241749.5A patent/CN103990386A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03186325A (en) * | 1989-11-30 | 1991-08-14 | Millipore Corp | Porous membrane formed of interstitial network of polymer and having hydrophilic surface |
| US5277812A (en) * | 1993-02-12 | 1994-01-11 | Gelman Sciences Inc. | Inter-penetrating network charge modified microporous membrane |
| CN101274227A (en) * | 2007-03-28 | 2008-10-01 | 宁波大学 | A kind of preparation method of polymer microfiltration membrane |
| CN102008898A (en) * | 2010-10-08 | 2011-04-13 | 亚美滤膜（南通）有限公司 | Method for preparing positive charge microfiltration membrane |
| CN102580572A (en) * | 2012-03-06 | 2012-07-18 | 中国科学技术大学 | Anion-exchange membrane and preparation method thereof |
| CN103446899A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Organic and inorganic surface chemically-crosslinked alginate-based hybrid hydrogel filter membrane, and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| A. GAREM ET AL.: "Selective Separation of Amino Acids with a Charged Inorganic Nanofiltration Membrane: Effect of Physicochemical Parameters on Selectivity", 《BIOTECHNOLOGY AND BIOENGINEERING》 * |
| 张景亚等: "浸渍-界面聚合法制备荷电镶嵌膜", 《高校化学工程学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109776831A (en) * | 2019-03-20 | 2019-05-21 | 福州大学 | A kind of fast preparation method of self-supporting hydroxide film and metal organic framework film |
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