CN108211800A - Pore membrane and clear opening membrane modifying method are led directly in a kind of modification - Google Patents
Pore membrane and clear opening membrane modifying method are led directly in a kind of modification Download PDFInfo
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- CN108211800A CN108211800A CN201810157500.4A CN201810157500A CN108211800A CN 108211800 A CN108211800 A CN 108211800A CN 201810157500 A CN201810157500 A CN 201810157500A CN 108211800 A CN108211800 A CN 108211800A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
- B01D2323/345—UV-treatment
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Abstract
The present invention provides a kind of modification and leads directly to pore membrane and clear opening membrane modifying method, the method includes：By regulating and controlling polyphenols, uniform function clad is formed in the surface and duct that lead directly to pore membrane in target, realizes the modification that pore membrane is led directly to the target, obtains modified straight-through pore membrane.The present invention is based on inertia leads directly to porous membrane material, it is acted on using the oxidation autohemagglutination of polyphenols in the solution, realize the modification of the surface that pore membrane is led directly to target and clear opening, it is simple for process, it is easy to operate, the problems such as process cycle of conventional film method of modifying is long, production cost is high and vulnerable can be effectively avoided, it is economic and environment-friendly so as to effectively reduce actual motion cost.
Description
Technical field
The present invention relates to membrane material processing technology fields, and pore membrane and straight-through pore membrane are led directly to more particularly, to a kind of modification
Method of modifying.
Background technology
In recent years, as the fields such as water process, bio-pharmaceuticals, food processing are constantly carried to what purification technique required
Height, membrane separation technique have received widespread attention as a kind of high efficiency, the isolation technics of low energy consumption and have obtained rapid hair
Exhibition.Meanwhile by seperation film carry out functionalization with realize target substance be precisely separated also become membrane technology a great development
Trend.
It is the straight-through pore membrane of representative as a kind of ultrafiltration membrane with special construction, uniform cylinder using trace-etching-film
Shape vertical through hole is provided for some unique properties, including membrane flux is big, retention characteristic is good and contamination resistance by force etc.
Excellent properties.But since this seperation film is typically to be processed by inert base film, inert basis material is in certain journey
The realization to its functionalized design is constrained on degree.
At present, the main path to solve the above problems is to be modified place to the surface of separation membrane material and duct
Reason, processing method mainly include：Physics cladding process, silane coupling agent method, wet chemistry modification, plasma/radiation treatment method etc..
Although these methods can realize the modification of membrane material, also all there are corresponding problems.
Wherein, although physics cladding process process is simple and with universality, easily come off failure in use；Silicon
Although alkane modification by coupling equally has universality, operating process is cumbersome；Wet chemistry modification has preferable modified effect, but
Operating process is complicated, and has specificity for different membrane material modified methods；And plasma/radiation treatment method has timeliness
Property, long-term modified effect of placing can be decreased obviously, and have high requirement to equipment.
It would therefore be highly desirable to develop, a kind of universality is relatively strong and the relatively simple method of operation, and clear opening is detached to realize
Effective modification of membrane material.
Invention content
In order to overcome the above problem or solve the above problems at least partly, the present invention provides a kind of modification and leads directly to pore membrane
And clear opening membrane modifying method, effectively to reduce modified operation difficulty, while ensure the universality of Modified Membrane and modified effect
Fruit.
On the one hand, the present invention provides a kind of method of modifying of straight-through pore membrane, including：By regulating and controlling polyphenols, in mesh
Uniform function clad is formed in the surface and duct of the straight-through pore membrane of mark, realizes and the target is led directly at the modification of pore membrane
Reason.
Wherein, it is described by regulating and controlling polyphenols, uniform work(is formed in the surface and duct that lead directly to pore membrane in target
It can further comprise the step of clad：S1, by the target lead directly to pore membrane be fixed on mold be immersed in together fill it is given
Reaction system is formed in the reaction unit of buffer solution, and vacuumize process gradually is carried out to the reaction system, until taking out true
The surface that target described in the decompression process of vacancy reason leads directly to pore membrane no longer generates bubble；S2, by polyphenols presoma
Ethanol/water solution and the ethanol/water solution of given oxidant are added dropwise to simultaneously in the reaction system, and are led directly in the target
Pore membrane both sides uniform stirring is to react fully；Deionized water and ethyl alcohol is used alternatingly to reacting sufficient target clear opening in S3
Film carries out washing by soaking, and carries out vacuum drying treatment at a given temperature, obtains in surface and duct and is respectively provided with balancing function
The straight-through pore membrane of clad.
Wherein, polyphenols presoma described in step S2 further be specially include dopamine, catechol and its
The Polyphenols object containing catechol based structures including derivative, pyrogallol and its derivative, levodopa and tannic acid
One kind in matter.
Wherein, it is specially further to include oxygen, ammonium persulfate, sodium metaperiodate, sulphur that oxidant is given described in step S2
Sour copper, silane coupling agent, molar ratio 1:Copper sulphate/the hydrogen peroxide mixture and molar ratio of (1~4) are 1:The oxygen of (1~4)
One kind in the substance with oxidisability including change copper/hydrogen peroxide mixture.
Wherein, described in step S2 in the ethanol/water solution of polyphenols presoma, the volume ratio of second alcohol and water is (0
~1):1, and the dosage of the polyphenols presoma is pressed per 1cm2Straight-through pore membrane corresponds to 5mg~40mg and gives；It is described given
In the ethanol/water solution of oxidant, the volume ratio of second alcohol and water is (0~1):1, and the dosage of the given oxidant is by every
Polyphenols presoma corresponds to 0.25mmol~1mmol and gives described in 1mmol.
Wherein, described in step S2 pore membrane both sides uniform stirring is led directly in the target so that in the abundant step of reaction,
Reaction temperature is 15~40 DEG C, the reaction time for 0.5~for 24 hours.
Further, before the step of S1, the method further includes：Inertia densification membrane material is placed in weight by S01
It is irradiated in ion accelerator, and sensitized treatment is carried out with ultraviolet light to the inertia densification membrane material after irradiation；S02, will be quick
Change that treated that inertia densification membrane material is fixed on mold, be placed in being etched in etching solution；S03, to completing
The inertia densification membrane material of etching process carries out washing by soaking, and the inertia densification membrane material completed at a given temperature to washing
Vacuum drying treatment is carried out, the straight-through pore membrane that the membrane aperture with target size is made leads directly to pore membrane as the target.
Wherein, etching solution described in step S02 includes：Temperature is 40 DEG C~65 DEG C, a concentration of 4mol/L~6.5mol/
The sodium hydroxide solution of L, a length of 5 minutes~60 minutes during the etching of the etching process；The step of S03, further wraps
It includes：Washing by soaking is carried out 3~4 times, and in room temperature to the inertia densification membrane material for completing etching process using deionized water
Under the inertia densification membrane material completed to the washing carry out vacuum drying treatment 12 hours, aperture is made as 100nm~5 μm
Straight-through pore membrane leads directly to pore membrane as the target.
Further, in step sl it is described by the target lead directly to pore membrane be fixed on mold be immersed in together fill to
Before the step of determining to form reaction system in the reaction unit of buffer solution, the method further includes：Buffering solute is dissolved in
It is (0~1) by volume ratio:Basis of formation buffer solution in the solvent that 1 ethanol/water solution is formed, and utilize 0.5mol/L's
The basic buffer solution is adjusted in hydrochloric acid, obtains pH value as the described of 5~9, a concentration of 10mmol/L~120mmol/L
Given buffer solution.
Wherein, the buffering solute is specially further disodium hydrogen phosphate/citric acid mixture, trishydroxymethylaminomethane
With one kind in sodium acetate or one group.
Wherein, reaction unit described in step S1 includes：Stainless steel reaction slot, organic glass with hollow sandwich structure
React capping, constant temperature circulating water system, stainless steel clamping mold, mechanical agitation system, magnetic agitation system；Wherein, in described
Empty sandwich connects the constant temperature circulating water system, passes through between the organic glass reaction capping and the stainless steel reaction slot
Rubber ring is sealed, and the center of organic glass reaction capping has clear opening, and the clear opening is for described in fixation
The agitating paddle of mechanical agitation system makes the agitating paddle be located at right over stainless steel clamping mold, the stainless steel clamping
Mold includes the upper side mould structure with reeded lower die structure and with the boss with the matching grooves, and described
It is fixed between lower die structure and the upper side mould structure by screw, the target leads directly to pore membrane and is placed in the groove simultaneously
It is fixed using the boss, the magnetic agitation system is located at immediately below the stainless steel reaction slot, for the mesh
The lower side reaction of the straight-through pore membrane of mark is stirred.
On the other hand, the present invention provides a kind of modification and leads directly to pore membrane, including membrane body, wherein the membrane body is using such as
The method of modifying of the upper straight-through pore membrane is prepared；Wherein, the thickness of the membrane body is 5 μm~50 μm, the film sheet
The density of clear opening is 10 in body5~108A/cm2, circle of the clear opening for a diameter of 100nm~5 μm, the membrane body
Surface and the clear opening in function clad thickness be 5nm~40nm.
Pore membrane and clear opening membrane modifying method are led directly in a kind of modification provided by the invention, based on target leads directly to pore membrane,
It is acted on using the oxidation autohemagglutination of polyphenols in the solution, at the modification for realizing the surface that pore membrane is led directly to target and clear opening
Reason.Present invention process is simple, easy to operate, can effectively avoid the process cycle length of conventional film method of modifying, production cost high
And the problems such as vulnerable, it is economic and environment-friendly so as to effectively reduce actual motion cost.
Description of the drawings
Fig. 1 is the flow for leading directly to pore membrane according to target is obtained in a kind of method of modifying of straight-through pore membrane of the embodiment of the present invention
Figure；
Fig. 2 be according in a kind of method of modifying of straight-through pore membrane of the embodiment of the present invention by regulating and controlling polyphenols to target
The flow chart that straight-through pore membrane is modified；
Fig. 3 is according to a kind of reaction unit schematic diagram of the method for modifying of straight-through pore membrane of the embodiment of the present invention.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with attached in the embodiment of the present invention
Figure, is clearly and completely described the technical solution in the present invention, it is clear that described embodiment is one of the present invention
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
All other embodiments obtained under the premise of creative work, shall fall within the protection scope of the present invention.
As the one side of the embodiment of the present invention, the present embodiment provides a kind of method of modifying of straight-through pore membrane, including：It is logical
Regulation and control polyphenols is crossed, uniform function clad is formed in the surface and duct that lead directly to pore membrane in target, is realized to described
Target leads directly to the modification of pore membrane.
It is to be understood that the present embodiment is to lead directly to pore membrane as basis material using target, basis material is positioned over reactant
In system, by regulating and controlling the polyphenols presoma added in into reaction system, and corresponding reaction condition is provided, make Polyphenols
In substrate material surface oxidation self-polymeric reaction occurs for substance, is formed in the surface and duct so as to lead directly to pore membrane in target uniform
Function clad realizes the modification that pore membrane is led directly to target.
Polyphenols therein can be the polyphenols containing catechol based structures using dopamine as representative,
And dopamine is a kind of endocrine neurotransmitter of organism.In weakly alkaline solution, the polyphenol containing catechol based structures
Class substance can occur to aoxidize self-polymeric reaction, and this self-polymeric reaction also can be neutral or even weak under the conditions of having existing for oxidant
It is carried out under conditions of acidity.
The self-polymeric reaction of polyphenols can be in the reaction system target clear opening film surface form a close attachment
Clad.There are still the phenolic hydroxyl group and amino isoreactivity group not reacted on this clad, these groups can not only
Enough improve the hydrophily of solid phase material, while also provide active site for the secondary function of material.
The method of modifying of a kind of straight-through pore membrane provided in an embodiment of the present invention, based on target leads directly to pore membrane, using more
The oxidation autohemagglutination effect of aldehydes matter in the solution, realizes the modification of the surface that pore membrane is led directly to target and clear opening.This
Invented technology is simple, easy to operate, can effectively avoid the process cycle length of conventional film method of modifying, production cost high and volatile
It is the problems such as effect, economic and environment-friendly so as to effectively reduce actual motion cost.
Further, it is formed described by regulating and controlling polyphenols, in the surface and duct that lead directly to pore membrane in target equal
Before the step of even function clad, the method further includes process flow as shown in Figure 1, and Fig. 1 is according to of the invention real
It applies and the flow chart that target leads directly to pore membrane is obtained in a kind of method of modifying of straight-through pore membrane of example, including：
Inertia densification membrane material is placed in heavy ion avcceleration and irradiates by S01, and to the inertia dense film after irradiation
Material carries out sensitized treatment with ultraviolet light；
Inertia densification membrane material after sensitized treatment is fixed on mold, is placed in being etched in etching solution by S02
Processing；
S03 carries out washing by soaking, and at a given temperature to having washed to the inertia densification membrane material for completing etching process
Into inertia densification membrane material carry out vacuum drying treatment, be made with target size membrane aperture straight-through pore membrane be used as described in
Target leads directly to pore membrane.
Specifically, in step S01, target is prepared as basis material using inertia densification membrane material and leads directly to pore membrane, first by base
Body material is positioned in heavy ion avcceleration, and radiation treatment is carried out to it using heavy ion avcceleration.As utilized84Kr is to matrix material
Material carries out irradiation operations.
Then, after the completion of to be irradiated, under the conditions of given sensitizing operation, such as sensitizing temperature, sensitization duration are preset
Under the conditions of, sensibilization is carried out to the basis material that irradiation is completed using ultraviolet light irradiation.For example, it is contemplated that film thickness etc. because
Element a length of 1 hour when setting is sensitized, utilizes ultraviolet lamp to carry out sensibilization to the basis material that irradiation is completed.
In step S02, under the conditions of given etching operation, such as type, concentration and the etching of given etching solution
Under the conditions of temperature, time etc., effect is etched to the inertia densification membrane material after sensibilization.Wherein etch (etching)
Refer to the technology for removing materials'use chemical reaction or physical shock effect.
Wherein, in one embodiment, etching solution described in step S02 includes：Temperature for 40 DEG C~65 DEG C, it is a concentration of
The sodium hydroxide solution of 4mol/L~6.5mol/L, a length of 5 minutes~60 minutes during the etching of the etching process.For example,
It is fine and close to the inertia after sensibilization using the sodium hydroxide solution of a concentration of 6.5mol/L under the conditions of 50 DEG C of etch temperature
The etching action of a length of 10 minutes when membrane material is etched.
In step S03, for completing the inertia densification membrane material of etching process according to above-mentioned steps, due to etched
Internal in journey there are impurity, and subsequent reactions can be had an impact.Therefore it needs to carry out the inertia densification membrane material that etching is completed
Washing, specifically after the etch is completed, washs inertia densification membrane material using given detergent.Such as consider reactant
Matter is repeatedly washed using deionized water, until the cleanliness factor of film reaches preset standard.The film it can be seen that obtaining is completed in washing
Clear opening with dispersion.
It after the completion of washing, also needs to carry out vacuum drying treatment to membrane material, to obtain dry membrane material.Specifically given
At a temperature of carry out vacuum drying operation, the dry film completed then has the membrane aperture of target size, then with target size film
The straight-through pore membrane in aperture leads directly to pore membrane as target.
Wherein optionally, the step of S03 further comprises：Using deionized water the lazy of etching process is completed to described
Property densification membrane material carry out washing by soaking 3~4 times, and the inertia densification membrane material completed at room temperature to the washing carry out it is true
Sky is dried 12 hours, and the straight-through pore membrane that aperture is made as 100nm~5 μm leads directly to pore membrane as the target.
Inertia makrolon dense film is used as in heavy ion avcceleration in one of the embodiments,84Kr ions into
Row irradiation makes film be damaged by nuclear track, and nuclear track membrane is obtained by the sensitization of ultraviolet lamp and the etching of NaOH.Etching process exists
50 DEG C, carry out in the NaOH solution of 6.25mol/L, reaction time 10min, reaction process ensures that solution fully stirs in system
It mixes.Deionized water washing by soaking is used after reaction 3~4 times, room temperature in vacuo drying 12h, the poly- carbon that obtained aperture is about 260nm
Acid esters leads directly to pore membrane.
In another embodiment, by inertia polyethylene terephthalate dense film as in heavy ion avcceleration,
With40Ar ions, which carry out irradiation, makes film be damaged by nuclear track, and nuclear track membrane is obtained by the sensitization of ultraviolet lamp and the etching of NaOH.
Etching process carries out in 65 DEG C, the NaOH solution of 4mol/L, and reaction time 60min, reaction process ensures solution in system
It is sufficiently stirred.Deionized water washing by soaking is used after reaction 3~4 times, room temperature in vacuo drying 12h, obtained aperture is about 4.5 μm
Polyethylene terephthalate lead directly to pore membrane.
Result of the test show preparation clear opening membrane pore size distribution it is uniform, pore size be 240~270nm, average pore size
For 260nm, and with the straight channels through entire film thickness, and inner wall smooth is clog-free.
It is wherein optional, it is described by regulating and controlling polyphenols, it is formed in the surface and duct that lead directly to pore membrane in target equal
Even function clad is further processed step with reference to figure 2, is according to a kind of modification side of straight-through pore membrane of the embodiment of the present invention
Lead directly to the flow chart that pore membrane is modified in method by regulating and controlling polyphenols to target, including：
S1, leads directly to pore membrane by the target and is fixed on and be immersed in the reaction unit for filling given buffer solution on mold together
Middle formation reaction system, and vacuumize process gradually is carried out to the reaction system, until in the decompression process of vacuumize process
The surface that the target leads directly to pore membrane no longer generates bubble；
The ethanol/water solution of polyphenols presoma and the ethanol/water solution of given oxidant are added dropwise to by S2 simultaneously
In the reaction system, and pore membrane both sides uniform stirring is led directly to react fully in the target；
S3, is used alternatingly deionized water and ethyl alcohol and leads directly to pore membrane to reacting sufficient target and carry out washing by soaking, and to
Determine to carry out vacuum drying treatment at temperature, obtain the straight-through pore membrane that balancing function clad is respectively provided in surface and duct.
It is to be understood that target clear opening membrane modifying is carried out using polyphenols self-polymeric reaction in the embodiment of the present invention
Principle is：Under the conditions of having existing for oxidant, quinoneization transformation, quinone and phenol can occur for the catechol group in polyphenols
Anti- disproportionated reaction occurs between hydroxyl, generates Semiquinone Radicals and causes crosslinking self-polymeric reaction.Meanwhile solid phase target leads directly to pore membrane
Surface exposure or absorption oxygen and nitrogen-atoms form hydrogen bond action with polyphenols, promote the crosslinking autohemagglutination of polyphenols
Reaction is led directly to porous membrane material surface in solid phase target and is carried out, so as to form the uniform cladding of poly- polyphenols in material surface
Layer, realizes the modification that pore membrane is led directly to target.
It is according to a kind of reaction unit schematic diagram of the method for modifying of straight-through pore membrane of the embodiment of the present invention, packet with reference to figure 3
It includes：Stainless steel reaction slot 301 with hollow sandwich structure 3011, organic glass reaction capping 302, constant temperature circulating water system
303rd, stainless steel clamping mold 304, mechanical agitation system 305, magnetic agitation system 306.
Wherein, hollow sandwich structure 3011 connects constant temperature circulating water system 303.Organic glass react capping 302 with it is stainless
It is sealed between steel reactive tank 301 by rubber ring, and the center of organic glass reaction capping 302 has clear opening 3021.Directly
Through-hole 3021 is used for the agitating paddle 3051 of solid mechanical stirring system 305, and agitating paddle 3051 is made to be located at stainless steel clamping mold 304
Surface.Stainless steel clamping mold 304 include with reeded lower die structure 3041 and with the matching grooves
The upper side mould structure 3042 of boss, and fixed between lower die structure 3041 and upper side mould structure 3042 by screw.Mesh
The straight-through pore membrane 307 of mark is placed in the groove and is fixed using the boss, and it is anti-that magnetic agitation system 306 is located at stainless steel
It answers immediately below slot 301, the lower side reaction that pore membrane 307 is led directly to target is realized by the control magneton 3061 of magnetic agitation system 306
Stirring.
In one of which embodiment, the stainless steel reaction slot 301 of reaction unit is cylinder, by hollow sandwich structure
Stainless steel material be made, interlayer connection constant temperature circulating water system 303 to carry out temperature control to reaction unit.Stainless steel reaction slot
The good buffer solution of configured in advance is filled in 301.The lid of stainless steel reaction slot 301, i.e. organic glass reaction capping 302 are circle
Shape is made of organic glass.There is clear opening 3021 at the center of organic glass reaction capping 302, while have placement agitating paddle
3051 and connect vacuum pump effect.Organic glass react between capping 302 and stainless steel reaction slot 301 by rubber ring into
Row sealing.The agitating paddle 3051 of mechanical agitation system 305 by clear opening 3021 be fixed on target lead directly to pore membrane 307 just on
Side realizes the stirring of side reaction on film.Magnetic agitation system 306 is placed in 301 lower section of stainless steel reaction slot, thus controls magneton real
Stirring on the downside of existing film.Stainless steel clamping mold 304 is made of in circular ring shape upper and lower two parts, respectively upper side mould structure
3042 and lower die structure 3041.Lower portion band is fluted to place membrane material, and upper portion is with matched
Boss is to fix membrane material.Rubber ring is accompanied between mold and membrane material to realize the fixation of film.Between two parts of mold by
Screw is fixed.The design of the device be in order under the premise of film planarization is not destroyed, take into account film both sides be sufficiently stirred and
Condition needed for the reaction of constant temperature.Meanwhile the use of the device can promote the progress of mass transport process in fenestra road, contribute in hole
Uniform poly- polyphenols clad is formed in road.
Specifically, using the reaction unit, it in step sl, will first of all for the planarization and concrete shape for ensureing film
Pending target leads directly to pore membrane and is fixed on ready mold, i.e., on the stainless steel clamping mold of above-mentioned reaction unit.So
Target is led directly to pore membrane afterwards to be immersed in pre-configured given buffer solution together with mold, which contains
It is placed in the reaction unit according to above-described embodiment, reaction unit, given buffer solution lead directly to pore membrane together with target and formed
Reaction system.Later, vacuumize process gradually is carried out to exclude the gas adsorbed in fenestra road to reaction system, until vacuumizing
Target leads directly to the surface of pore membrane and no longer generates bubble in the decompression process of processing, and the gas for illustrating to adsorb in fenestra road has excluded to do
Only, vacuum environment is formed.
In one of the embodiments, in step sl it is described the target is led directly to pore membrane and is fixed on mold soak together
Not in the reaction unit for filling given buffer solution before middle the step of forming reaction system, the method further includes：It will be slow
It is (0~1) to rush solute and be dissolved in by volume ratio:Basis of formation buffer solution in the solvent that 1 ethanol/water solution is formed, and profit
The basic buffer solution is adjusted with the hydrochloric acid of 0.5mol/L, obtain pH value for 5~9, a concentration of 10mmol/L~
The given buffer solution of 120mmol/L.
It is molten first to carry out given buffering it is to be understood that before vacuumize process is carried out to target clear opening for the present embodiment
The configuration of liquid.Specifically in above-mentioned reaction unit, it using ethanol/water solution as solvent, will can be used to that the slow of buffer solution is configured
It rushes solute and is added to the basic buffer solution of configuration in the solvent, and its pH value is adjusted with hydrochloric acid.
Wherein, it is (0~1) as the volume ratio of the ethanol/water solution of solvent:1.
Wherein, the buffering solute is specially further disodium hydrogen phosphate/citric acid mixture, trishydroxymethylaminomethane
With one kind in sodium acetate or one group.
It is to be understood that the substance as buffering solute is specially further the object that can form buffer solution in the solution
Matter, the substance include but not limited to disodium hydrogen phosphate/citric acid mixture, trishydroxymethylaminomethane and sodium acetate etc..
Wherein, for carrying out a concentration of 0.5mol/L of the hydrochloric acid of pH value adjusting.Adjusting the given buffer solution completed is
PH value is 5~9, the buffer solution of a concentration of 10mmol/L~120mmol/L.
In step s 2, above-mentioned steps are completed with the reaction system of vacuumize process, while thereto with the side of instillation
Formula is slowly added to the ethanol/water solution of polyphenols presoma and the ethanol/water solution of given oxidant.Then using above-mentioned
Reaction unit is sufficiently stirred in film both sides, and reaction system is made to be reacted under conditions of being sufficiently stirred, until fully anti-
It should.
Wherein, described in step S2 pore membrane both sides uniform stirring is led directly in the target so that in the abundant step of reaction,
Reaction temperature is 15~40 DEG C, the reaction time for 0.5~for 24 hours.Reaction starts timing when starting, and the reaction time terminates, it is believed that
Fully reaction.
Wherein optional, polyphenols presoma described in step S2 is specially further to include dopamine, adjacent benzene two
Contain the more of catechol based structures including phenol and its derivative, pyrogallol and its derivative, levodopa and tannic acid
One kind in aldehydes matter.
It is to be understood that the polyphenols presoma in the present embodiment, which is specifically chosen for one kind, contains catechol base junction
The polyphenols of structure.Such polyphenols include but not limited to dopamine, catechol and its derivative, pyrogallol and
Its derivative, levodopa and tannic acid etc..
In one of the embodiments, described in step S2 in the ethanol/water solution of polyphenols presoma, ethyl alcohol and
The volume ratio of water is (0~1):1, and the dosage of the polyphenols presoma is pressed per 1cm2Straight-through pore membrane correspond to 5mg~
40mg gives.
Wherein optional, it is specially further to include oxygen, ammonium persulfate, periodic acid that oxidant is given described in step S2
Sodium, copper sulphate, silane coupling agent, molar ratio 1:Copper sulphate/the hydrogen peroxide mixture and molar ratio of (1~4) are 1:(1~
4) one kind in the substance with oxidisability including copper oxide/hydrogen peroxide mixture.
It is to be understood that the oxidant in the present embodiment is specifically chosen for a kind of substance with oxidisability, the substance packet
It includes but is not limited to oxygen, ammonium persulfate, sodium metaperiodate, copper sulphate, silane coupling agent, molar ratio 1:The copper sulphate of (1~4)/
Hydrogen peroxide mixture and molar ratio are 1:Copper oxide/the hydrogen peroxide mixture of (1~4) etc..
Wherein, in one embodiment, in the ethanol/water solution of the given oxidant, the volume ratio of second alcohol and water is
(0~1):1, and the dosage of the given oxidant as corresponded to per polyphenols presoma described in 1mmol 0.25mmol~
1mmol gives.
In step s3, after above-mentioned steps are fully reacted, target lead directly to pore membrane surface and through-hole in form
Even clad.In order to make film surface pure, after fully being reacted according to above-mentioned steps, with deionized water and ethyl alcohol alternate immersion
It washs the target with clad and leads directly to pore membrane.It can washing by soaking 3~4 times repeatedly.
Then, the straight-through pore membrane completed to washing, carries out vacuum drying treatment at a given temperature.As carried out at room temperature
Vacuum drying treatment.In addition vacuum drying time can be arranged as required to, such as 12 hours.Vacuum drying treatment is completed, i.e., complete
The complete modified flow of pore membrane is led directly into target.Uniform function cladding is respectively provided in the clear opening film surface of acquisition and duct
Layer, the straight-through pore membrane are modified straight-through pore membrane.
A kind of method of modifying of straight-through pore membrane provided in an embodiment of the present invention contains catechol base junction using dopamine etc.
The polyphenols of structure leads directly to target pore membrane and is modified processing, and since dopamine chemical modification has, universality is strong, reacts
The advantages that mild condition and method facilitate, can realize the quick modification in clear opening film surface and duct.
In one embodiment according to above-described embodiment, the trihydroxy methyl amino of 10mmol/L is configured in reaction unit
Methane buffer solution, solvent are deionized water, with the salt acid for adjusting pH of 0.5mol/L to 8.5；By poly- carbon obtained in embodiment 1
Acid esters leads directly to pore membrane and is immersed in vacuumize process in buffer solution, excludes the gas in fenestra road；Under conditions of being sufficiently stirred,
Dopamine hydrochloride solution is added drop-wise in reaction system, the dopamine hydrochloride dosage is more per 1L buffer solutions addition 2g
Bar amine hydrochlorate；It is reacted under the conditions of 25 DEG C for 24 hours, treats to use deionized water washing by soaking after reaction 3~4 times, room temperature in vacuo
Dry 12h, the modification coating thickness about 30nm of acquisition.
In another embodiment, the trishydroxymethylaminomethane buffer solution of 10mmol/L is configured in reaction unit,
Solvent is that volume ratio is 1:1 ethanol/water mixed solution, with the salt acid for adjusting pH of 0.5mol/L to 8.5；It will be made in embodiment 1
The makrolon obtained leads directly to pore membrane and is immersed in vacuumize process in buffer solution, excludes the gas in fenestra road；It is being sufficiently stirred
Under conditions of, levodopa solution is added drop-wise in reaction system, the levodopa dosage is to add in 1g per 1L buffer solutions
Levodopa, solvent are that volume ratio is 1:1 ethanol/water mixed solution；8h is reacted under the conditions of 15 DEG C, treats to use after reaction
Deionized water and ethyl alcohol alternate immersion wash 3~4 times, room temperature in vacuo drying 12h, the modification coating thickness about 5nm of acquisition.
In yet another embodiment, in reaction unit be configured 50mmol/L sodium acetate buffer, solvent for go from
Sub- water, with the salt acid for adjusting pH of 0.5mol/L to 5.0；Makrolon obtained in embodiment 1 is led directly into pore membrane and is immersed in buffering
Vacuumize process in solution excludes the gas in fenestra road；Under conditions of being sufficiently stirred, by dopamine hydrochloride aqueous solution and
Sodium metaperiodate aqueous solution is added drop-wise in reaction system, and the dopamine hydrochloride dosage is to add in 2g dopamines per 1L buffer solutions
Hydrochloride, sodium metaperiodate dosage are to add in 4.3g sodium metaperiodates per 1L buffer solutions；2h is reacted under the conditions of 25 DEG C, treats reaction knot
Shu Houyong deionized waters washing by soaking 3~4 times, room temperature in vacuo drying 12h, the modification coating thickness about 20nm of acquisition.
In yet another embodiment, disodium hydrogen phosphate-citric acid solution that pH is 5.5 is configured in reaction unit,
Solvent is deionized water, wherein a concentration of 113.75mmol/L of disodium hydrogen phosphate, citric acid concentration 43.125mmol/L；It will be real
It applies makrolon obtained in example 1 and leads directly to pore membrane and be immersed in vacuumize process in buffer solution, exclude the gas in fenestra road；
Under conditions of being sufficiently stirred, dopamine hydrochloride aqueous solution and ammonium persulfate aqueous solution are added drop-wise in reaction system, it is described more
Bar amine hydrochlorate dosage is that 2g dopamine hydrochlorides are added in per 1L buffer solutions, and ammonium persulfate dosage is to be added in per 1L buffer solutions
1.2g ammonium persulfate；2h is reacted under the conditions of 25 DEG C, treats to use deionized water washing by soaking after reaction 3~4 times, room temperature in vacuo
Dry 12h, the modification coating thickness about 40nm of acquisition.
In yet another embodiment, the trishydroxymethylaminomethane buffer solution of 50mmol/L is configured in reaction unit,
Solvent is deionized water, with the salt acid for adjusting pH of 0.5mol/L to 8.5；Makrolon obtained in embodiment 1 is led directly into pore membrane
Vacuumize process in buffer solution is immersed in, excludes the gas in fenestra road；Under conditions of being sufficiently stirred, by dopamine hydrochloric acid
The aqueous solution of saline solution and copper sulphate and hydrogen peroxide is added drop-wise in reaction system, and the dopamine hydrochloride dosage is per 1L
Buffer solution adds in 2g dopamine hydrochlorides, and copper sulphate dosage is that 0.8g copper sulphate is added in per 1L buffer solutions, and hydrogen peroxide is used
It measures and adds in 19.6mmol hydrogen peroxide for every 1L buffer solutions；React 0.5h under the conditions of 35 DEG C, treat to spend after reaction from
Sub- water washing by soaking 3~4 times, room temperature in vacuo drying 12h, the modification coating thickness about 20nm of acquisition.
The experimental results showed that method of modifying according to embodiments of the present invention, the modification clad of modified acquisition is uniform
It is smooth, be not in extensive agglomeration, the duct of straight-through pore membrane will not be blocked, and the modification clad in fenestra road is equal
It is even smooth, it is close to hole wall, duct will not be blocked.
In yet another embodiment, respectively by the aperture according to made from above-described embodiment be about 260nm makrolon it is straight
The modification of through-hole membrane material, modified coating thickness about 30nm leads directly to porous membrane material and is modified changing for coating thickness about 20nm
Property leads directly to porous membrane material and is placed in contact angle tester, and the water contact angle on membrane material surface is measured with sessile drop method.
Its water contact angle is from originally after measurement result shows makrolon clear opening membrane modifying according to embodiments of the present invention
91.1 ° be reduced to 61.6 ° and 39.3 ° hereinafter, the modified membrane material water contact angle of explanation is obviously reduced, film it is hydrophilic
Property improve.
In yet another embodiment, the makrolon clear opening for being about 260nm by the aperture according to made from above-described embodiment
The modification of membrane material and modified coating thickness about 5nm are led directly to porous membrane material and are placed on folder membrane type nutsch filter, in 0.1 atmospheric pressure
Transmembrane pressure under with deionized water measure membrane material cross-film water flux.
Result of the test shows that the cross-film water flux of above-mentioned straight-through porous membrane material under this condition is about 3.7L/m2S, and
The cross-film water flux of modified modified membrane under this condition is about 4.6L/m2·s.In the operation item of identical transmembrane pressure
Under part, the liquid phase cross-film propagated flux of modified straight-through pore membrane improves more than 25% according to the method for the embodiment of the present invention.
As the other side of the embodiment of the present invention, the present embodiment provides a kind of modifications to lead directly to pore membrane, including membrane body.
Wherein, the membrane body is prepared using the method for modifying of the straight-through pore membrane as described in above-described embodiment.
It is to be understood that it is to be the straight-through pore membrane that represents as matrix using nuclear track membrane that pore membrane is led directly in the modification of the present embodiment
Material, using the clear opening membrane modifying method of above-described embodiment, prepared by processing is modified to basis material.Obtained
In the membrane body of modified straight-through pore membrane there is the clear opening of dispersion, there is uniform function cladding in the surface and duct of membrane body
Layer.
Wherein, the thickness of the membrane body is 5 μm~50 μm, and the density of clear opening is 10 in the membrane body5~108A/
cm2, the clear opening is the circle of a diameter of 100nm~5 μm, and function coats in the surface of the membrane body and the clear opening
The thickness of layer is 5nm~40nm.
Pore membrane is led directly in a kind of modification provided in an embodiment of the present invention, based on leading directly to pore membrane by target, utilizes polyphenol
The oxidation autohemagglutination effect of class substance in the solution, realizes and the surface of pore membrane and the modification of clear opening is led directly to target and is made.This
Presence of the pore membrane due to great amount of hydroxy group and amino in polyphenols clad, membrane material are led directly in the modification that inventive embodiments provide
Hydrophily greatly improve, so as to which trans-membrane flux in water treatment procedure is greatly improved.Also, in surface and duct
The poly- Polyphenols clad formed can be waited as the platform of film secondary function by Michael's addition or schiff base reaction
Journey introduces small molecule, polymer or biomolecule and carries out secondary function, realizes selectivity point of the seperation film for target substance
From.
In addition, those skilled in the art it should be understood that the present invention application documents in, term " comprising ",
"comprising" or any other variant thereof is intended to cover non-exclusive inclusion, so that the process including a series of elements,
Method, article or equipment not only include those elements, but also including other elements that are not explicitly listed or also wrap
It includes as elements inherent to such a process, method, article, or device.In the absence of more restrictions, by sentence " including
One ... " element that limits, it is not excluded that also exist in the process, method, article or apparatus that includes the element another
Outer identical element.
In the specification of the present invention, numerous specific details are set forth.It should be understood, however, that the embodiment of the present invention can
To put into practice without these specific details.In some instances, well known method, structure and skill is not been shown in detail
Art, so as not to obscure the understanding of this description.Similarly, it should be understood that disclose in order to simplify the present invention and helps to understand respectively
One or more of a inventive aspect, above in the description of exemplary embodiment of the present invention, each spy of the invention
Sign is grouped together into sometimes in single embodiment, figure or descriptions thereof.
It is intended to however, should not explain the method for the disclosure in reflection is following：That is the claimed invention requirement
The more features of feature than being expressly recited in each claim.More precisely, as claims are reflected
Like that, inventive aspect is all features less than single embodiment disclosed above.Therefore, it then follows the power of specific embodiment
Thus sharp claim is expressly incorporated in the specific embodiment, wherein each claim is in itself as independent reality of the invention
Apply example.
Finally it should be noted that：The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
The present invention is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that：It still can be right
Technical solution recorded in foregoing embodiments modifies or carries out equivalent replacement to which part technical characteristic；And this
A little modifications are replaced, the spirit and model of various embodiments of the present invention technical solution that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (12)
1. a kind of method of modifying of straight-through pore membrane, which is characterized in that including：By regulating and controlling polyphenols, in target clear opening
Uniform function clad is formed in the surface and duct of film, realizes the modification that pore membrane is led directly to the target.
2. according to the method described in claim 1, it is characterized in that, described by regulating and controlling polyphenols, in target clear opening
The step of forming uniform function clad in the surface and duct of film further comprises：
The target is led directly to pore membrane and is fixed on shape in the reaction unit for being immersed in together on mold and filling given buffer solution by S1
Into reaction system, and vacuumize process gradually is carried out to the reaction system, until described in the decompression process of vacuumize process
The surface that target leads directly to pore membrane no longer generates bubble；
The ethanol/water solution of polyphenols presoma and the ethanol/water solution of given oxidant are added dropwise to described by S2 simultaneously
In reaction system, and pore membrane both sides uniform stirring is led directly to react fully in the target；
S3 is used alternatingly deionized water and ethyl alcohol and leads directly to pore membrane progress washing by soaking to reacting sufficient target, and to constant temperature
Degree is lower to carry out vacuum drying treatment, obtains the straight-through pore membrane that balancing function clad is respectively provided in surface and duct.
3. according to the method described in claim 2, it is characterized in that, polyphenols presoma described in step S2 further has
Body is containing including dopamine, catechol and its derivative, pyrogallol and its derivative, levodopa and tannic acid
There is one kind in the polyphenols of catechol based structures.
4. according to the method described in claim 3, it is characterized in that, it is specially further to wrap that oxidant is given described in step S2
Include oxygen, ammonium persulfate, sodium metaperiodate, copper sulphate, silane coupling agent, molar ratio 1:Copper sulphate/the hydrogen peroxide of (1~4)
Mixture and molar ratio are 1:One in the substance with oxidisability including the copper oxide/hydrogen peroxide mixture of (1~4)
Kind.
5. according to the method described in claim 4, it is characterized in that, the ethyl alcohol of polyphenols presoma described in step S2/
In aqueous solution, the volume ratio of second alcohol and water is (0~1):1, and the dosage of the polyphenols presoma is pressed per 1cm2It is straight-through
Pore membrane corresponds to 5mg~40mg and gives；
In the ethanol/water solution of the given oxidant, the volume ratio of second alcohol and water is (0~1):1, and the given oxidant
Dosage polyphenols presoma as described in every 1mmol correspond to 0.25mmol~1mmol and give.
6. according to the method described in claim 2, it is characterized in that, in the target to lead directly to pore membrane both sides described in step S2 equal
Even to stir so that in the abundant step of reaction, reaction temperature is 15~40 DEG C, the reaction time for 0.5~for 24 hours.
7. according to the method described in claim 2, it is characterized in that, before the step of S1, further include：
Inertia densification membrane material is placed in heavy ion avcceleration and irradiates by S01, and to the inertia densification membrane material after irradiation
Sensitized treatment is carried out with ultraviolet light；
Inertia densification membrane material after sensitized treatment is fixed on mold, is placed in being etched place in etching solution by S02
Reason；
S03 carries out washing by soaking to the inertia densification membrane material for completing etching process, and washing is completed at a given temperature
Inertia densification membrane material carries out vacuum drying treatment, and the straight-through pore membrane of the membrane aperture with target size is made as the target
Straight-through pore membrane.
8. the method according to the description of claim 7 is characterized in that etching solution described in step S02 includes：Temperature is 40 DEG C
~65 DEG C, the sodium hydroxide solution of a concentration of 4mol/L~6.5mol/L, a length of 5 minutes~60 during the etching of the etching process
Minute；
The step of S03, further comprises：
Washing by soaking is carried out 3~4 times, and in room temperature to the inertia densification membrane material for completing etching process using deionized water
Under the inertia densification membrane material completed to the washing carry out vacuum drying treatment 12 hours, aperture is made as 100nm~5 μm
Straight-through pore membrane leads directly to pore membrane as the target.
9. according to the method described in claim 5, it is characterized in that, described in step sl lead directly to pore membrane by the target and fix
Before the step of reaction system is formed in being immersed in the reaction unit for filling given buffer solution on mold together, further include：
It is (0~1) that buffering solute, which is dissolved in by volume ratio,:Basis of formation buffering is molten in the solvent that 1 ethanol/water solution is formed
Liquid, and the basic buffer solution being adjusted using the hydrochloric acid of 0.5mol/L, obtain pH value for 5~9, it is a concentration of
The given buffer solution of 10mmol/L~120mmol/L.
10. according to the method described in claim 9, it is characterized in that, it is described buffering solute further be specially disodium hydrogen phosphate/
One kind in citric acid mixture, trishydroxymethylaminomethane and sodium acetate or one group.
11. according to the method any in claim 2-10, which is characterized in that reaction unit includes described in step S1：
Stainless steel reaction slot with hollow sandwich structure, organic glass reaction capping, constant temperature circulating water system, stainless steel clamping mould
Tool, mechanical agitation system, magnetic agitation system；
Wherein, the hollow sandwich structure connects the constant temperature circulating water system, the organic glass reaction capping with it is described not
It is sealed between rust steel reactive tank by rubber ring, and the center of organic glass reaction capping has clear opening, it is described straight
Through-hole is used to fix the agitating paddle of the mechanical agitation system, make the agitating paddle be located at the stainless steel clamp mold just on
Side, the stainless steel clamping mold are included with reeded lower die structure and with the upper of the boss with the matching grooves
Side mould structure, and fixed between the lower die structure and the upper side mould structure by screw, the target clear opening
Film is placed in the groove and is fixed using the boss, and the magnetic agitation system is being located at the stainless steel reaction slot just
Lower section, the lower side reaction for leading directly to pore membrane to the target are stirred.
12. pore membrane is led directly in a kind of modification, including membrane body, which is characterized in that the membrane body is using such as claim 1-11
In any method be prepared；
Wherein, the thickness of the membrane body is 5 μm~50 μm, and the density of clear opening is 10 in the membrane body5~108A/cm2,
The clear opening is the circle of a diameter of 100nm~5 μm, function clad in the surface of the membrane body and the clear opening
Thickness is 5nm~40nm.
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| CN111545172A (en) * | 2020-05-11 | 2020-08-18 | 清华大学 | Supported adsorbent and preparation method and application thereof |
| CN113956793A (en) * | 2020-09-07 | 2022-01-21 | 清华大学 | Metal-polyphenol coating and preparation method thereof |
| CN114588787A (en) * | 2022-01-20 | 2022-06-07 | 清华大学 | Method for modifying inner wall of straight-through hole membrane channel by using metal-polyphenol |
| CN118122138A (en) * | 2024-04-30 | 2024-06-04 | 湖南叶之能科技有限公司 | Microporous membrane and preparation method and application thereof |
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