CN107694354A - A kind of polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method - Google Patents
A kind of polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method Download PDFInfo
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- CN107694354A CN107694354A CN201710829959.XA CN201710829959A CN107694354A CN 107694354 A CN107694354 A CN 107694354A CN 201710829959 A CN201710829959 A CN 201710829959A CN 107694354 A CN107694354 A CN 107694354A
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- pvdf
- ultrafiltration membrane
- polyvinylidene fluoride
- membrane surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The present invention relates to a kind of polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method, including：Pvdf membrane surface is set to form C=C double bonds PVDF ultrafiltration membrane progress alkali process, progress negative electrical charge, which handles to obtain, afterwards carries SO3 ‑The pvdf membrane of ion, finally carry out sulphur aminating reaction and obtain the PVDF ultrafiltration membrane of surface modification.The PVDF ultrafiltration membrane that method of modifying provided by the invention obtains, surface carries a large amount of positive charges, compared with unmodified PVDF ultrafiltration membrane, salt rejection rate (resistance metal ion performance) is minimum to improve 6 times, film wire antifouling property significantly improves, service life is longer, and the method for modifying cost is cheap, save space, method is simple, is easy to industrialization.
Description
Technical field
The present invention relates to technical field of membrane, and in particular to a kind of Kynoar (PVDF) method for modifying surface of ultrafiltration membrane.
Background technology
Membrane separation technique is a kind of efficient, environmental protection, the separation method of energy-conservation, including counter-infiltration (RO), nanofiltration (NF), micro-filtration
(MF), the technology such as ultrafiltration (UF), is widely used in desalinization, sewage disposal, food, medicine, biology, chemical industry, electronics, energy
The fields such as source, its core are seperation films.
Kynoar is due to excellent chemical stability, against weather, resistance tocrocking, radiation hardness and easy film forming etc.
Advantage, it is the preferred material of milipore filter.However, in industrial wastewater, typically contain substantial amounts of copper, chromium, nickel, lead, mercury etc. and carry
The metal ion of positive charge, substantial pollution can be caused to ultrafiltration membrane filaments surface, cause flux to reduce, film service life shortens, most
Extra matting and membrane separating process cost are dramatically increased at last.Therefore, ultrafiltration membrane filaments surface is modified, solves to divide
From the membrane pollution problem of film, turn into the focus of current ultrafiltration membrane filaments R＆D work.
Have been reported that and physical modification, surface chemical modification (chemical surface treatment, surface graft modification are coated by surface
Deng) and improve its anti-fouling performance the methods of blending and modifying.As Chinese patent CN106422821A is disclosed, one kind is hydrophilic to be changed
The preparation method of property polyvinylidene fluoride (PVDF) ultrafiltration membrane, includes the preparation and its surface chemical modification of polyvinylidene fluoride (PVDF) ultrafiltration membrane.Pass through
Electrostatic spinning process prepares polyvinylidene fluoride (PVDF) ultrafiltration membrane, after alkali process, uses free radical polymerisation process by concentration for 10-20%
Acrylic acid-grafted to pass through alkali process PVDF ultrafiltration membrane surface, the hydrophily on improvement film surface.But do not referred in the patent
Repellence of the modified polyvinylidene fluoride (PVDF) ultrafiltration membrane to metal ion.
The content of the invention
For deficiency of the prior art, the present invention carries out surface modification using pure chemistry method to PVDF ultrafiltration membrane, leads to
Cross grafting polyamino polymer, assign the substantial amounts of positive charge of ultrafiltration membrane surface, so as to carried in sewage the metal of positive charge from
Son produces stronger repulsive interaction, improves the antifouling property of milipore filter, extends its service life.
To reach above-mentioned purpose, the technical solution adopted by the present invention is as follows：
A kind of polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method, including：
1) pvdf membrane surface is made to form C=C double bonds PVDF ultrafiltration membrane progress alkali process；
2) the pvdf membrane progress negative electrical charge with C=C double bonds is handled to obtain and carries SO3 -The PVDF ultrafiltration membrane of ion；
3) SO will be carried3 -The pvdf membrane of ion carries out sulphur aminating reaction and obtains the PVDF ultrafiltration membrane of surface modification.
In above-mentioned surface modifying method, alkali process described in step 1) is in NaOH and KMnO4Mixed aqueous solution in enter
Capable, the mass fraction of mixed aqueous solution is 36%, the NaOH and KMnO4Mass ratio be 8:1.
Further, the temperature of alkali process described in step 1) is 50 DEG C, processing time 90min.
In above-mentioned surface modifying method, the processing of negative electrical charge described in step 2) is in NaHSO3And H2SO4Mixed aqueous solution
Progress, the mass fraction of mixed aqueous solution is 4%, the NaHSO3And H2SO4Mass ratio be 1:1.
Further, the temperature of the processing of negative electrical charge described in step 2) is room temperature, processing time 30min.
In above-mentioned surface modifying method, sulphur aminating reaction described in step 3) is in polyamino polymer and SOCl2It is mixed
Carried out in Heshui solution, the mass fraction of mixed aqueous solution is 36%, the polyamino polymer and SOCl2Mass ratio be
1:1。
Further, the pH value of sulphur aminating reaction described in step 3) is controlled between 6.0-8.5, it is preferred that pH value control
System is 7.0.
Further, sulfanilamide (SN) reaction temperature described in step 3) is room temperature, reaction time 60-300min, it is preferred that
Reaction time is controlled in 90-150min, such as：90min, 100min, 110min, 120min, 130min, 140min or 150min
Deng.
In the present invention, the polyamino polymer refers to side chain or side chain contains polymer compared with polyamino.
In embodiments of the present invention, the polynary Ammonia polymer is selected from poly- (N- (N- (2- amino-ethyls) -2- amino
Ethyl) aspartic acid)-(I), polylysine-(II), poly- (2- amidoethyl methacrylates)-(III), poly arginine-
(IV) one or more in, concrete structure is as follows, the degree of polymerization：200≤n≤400, but be not limited to it is above-mentioned enumerate it is more
First Ammonia polymer, other polynary Ammonia polymer that can reach same effect commonly used in the art can also be used for the present invention.
Heretofore described " room temperature " refers to 20-25 DEG C of temperature.
Unless explicitly stated otherwise in contrast, otherwise, all scopes that the present invention quotes include end value.For example, " during reaction
Between be 60-300min ", represent the sulfanilamide (SN) reaction time span be 60min≤T≤300min.
Terminology used in the present invention "one" or " one kind " describes key element and component described herein.So do only
It is for convenience, and to provide general meaning to the scope of the present invention.This description should be read to include one or extremely
It is few one, and the odd number also includes plural number, is anticipated unless significantly separately referring to him.
Numeral in the present invention is approximation, no matter whether uses the wording such as " about " or " about ".The numerical value of numeral has
It is possible that the difference such as 1%, 2%, 5%, 7%, 8%, 10%.It is any to have whenever a numeral with N values is disclosed
The numeral that N+/- 1%, N+/- 2%, N+/- 3%, N+/- 5%, N+/- 7%, N+/- 8% or N+/- 10% are worth can be by clearly public
Open, wherein " +/- " refers to add deduct, and the scope between N-10% to N+10% is also disclosed.
Unless otherwise defined, the otherwise implication of all scientific and technical terminologies used herein and common skill of the art
As art personnel are generally understood that.Although similar or equivalent method and material also can use with approach described herein and material
In the implementation or test of embodiment of the present invention, but suitable method and material is described below.What is be mentioned above is all
Publication, patent application, patent and other bibliography are incorporated herein in a manner of being cited in full text, except non-quoted physical segment
Fall.If conflict occurs, it is defined by this specification and its included definition.In addition, material, method and embodiment are only exemplary
, it is no intended to limited.
The beneficial effects of the present invention are：
(1) method of modifying provided by the invention obtains the positively charged PVDF ultrafiltration membrane in surface, surpasses with unmodified PVDF
Filter membrane is compared, and salt rejection rate (resistance metal ion performance) is minimum to improve 6 times, and film wire antifouling property significantly improves；
(2) present invention uses pure chemistry method of modifying, and compared with physics coats method of modifying, obtained film wire performance is more steady
Fixed, service life is longer；
(3) surface modifying method cost provided by the invention is cheap, save space, method is simple, is easy to industrialization.
Brief description of the drawings
Fig. 1：PVDF ultrafiltration membrane surface is modified flow chart
Wherein：(I), poly- (N- (N- (2- amino-ethyls) -2- amino-ethyls) aspartic acid)；(II), polylysine；
(III), poly- (2- amidoethyl methacrylates)；(IV), poly arginine.
Embodiment
As described below is the preferred embodiment of the present invention, and what the present invention was protected is not limited to the following side of being preferable to carry out
Formula.It should be pointed out that for those skilled in the art on the basis of this innovation and creation design, some deformations for making and
Improve, belong to protection scope of the present invention, in order to further describe the present invention, illustrate with reference to specific embodiment.
Embodiment 1
1) wet spinning self-control PVDF hollow fiber ultrafiltration membranes；
2) PVDF hollow fiber ultrafiltration membranes are immersed into NaOH/KMnO4In=8/1 aqueous solution (mass fraction 36%),
90min is reacted at 50 DEG C；
3) pvdf membrane prepared by 2) step is immersed into NaHSO again3/H2SO4(mass fraction is=1/1 aqueous solution
4%) in, 30min is reacted at room temperature；
4) pvdf membrane prepared by 3) step is finally immersed in poly- (N- (N- (2- amino-ethyls) -2- amino-ethyls)
Aspartic acid)/SOCl2In=1/1 aqueous solution (mass fraction 36%), sulphur aminating reaction 90min occurs at room temperature, and adjust
PH value produces the positively charged PVDF hollow fiber ultrafiltration membranes in surface 7.0 or so.
Embodiment 2
1) wet spinning self-control PVDF hollow fiber ultrafiltration membranes；
2) PVDF hollow fiber ultrafiltration membranes are immersed into NaOH/KMnO4In=8/1 aqueous solution (mass fraction 36%), in
90min is reacted at 50 DEG C；
3) pvdf membrane prepared by 2) step is immersed into NaHSO again3/H2SO4(mass fraction is=1/1 aqueous solution
4%) in, 30min is reacted at room temperature；
4) pvdf membrane immersion polylysine/SOCl that 3) prepared by step will finally be passed through2=1/1 aqueous solution (quality
Fraction be 36%) in, sulphur aminating reaction 90min occurs at room temperature, and adjust pH value 7.0 or so, produces surface positively charged
The PVDF hollow fiber ultrafiltration membranes of lotus.
Embodiment 3
1) wet spinning self-control PVDF hollow fiber ultrafiltration membranes；
2) PVDF hollow fiber ultrafiltration membranes are immersed into NaOH/KMnO4In=8/1 aqueous solution (mass fraction 36%),
90min is reacted at 50 DEG C；
3) pvdf membrane prepared by 2) step is immersed into NaHSO again3/H2SO4(mass fraction is=1/1 aqueous solution
4%) in, 30min is reacted at room temperature；
4) poly- (2- the amidoethyl methacrylates)/SOCl of pvdf membrane immersion that 3) prepared by step will finally be passed through2=
In 1/1 aqueous solution (mass fraction 36%), sulphur aminating reaction 90min occurs at room temperature, and it is left 7.0 to adjust pH value
The right side, produce the positively charged PVDF hollow fiber ultrafiltration membranes in surface.
Embodiment 4
1) wet spinning self-control PVDF hollow fiber ultrafiltration membranes；
2) PVDF hollow fiber ultrafiltration membranes are immersed into NaOH/KMnO4In=8/1 aqueous solution (mass fraction 36%),
90min is reacted at 50 DEG C；
3) pvdf membrane prepared by 2) step is immersed into NaHSO again3/H2SO4(mass fraction is=1/1 aqueous solution
4%) in, 30min is reacted at room temperature；
4) pvdf membrane immersion poly arginine/SOCl that 3) prepared by step will finally be passed through2=1/1 aqueous solution (quality point
Number adjusts pH value 7.0 or so in 36%), sulphur aminating reaction 90min occurs at room temperature, and it is positively charged to produce surface
PVDF hollow fiber ultrafiltration membranes.
Comparative example 1
Wet spinning makes PVDF hollow fiber ultrafiltration membranes by oneself, without any surface chemical modification.
The performance test of embodiment 5
Unmodified PVDF ultrafiltration prepared by the PVDF ultrafiltration membrane and comparative example 1 that surface prepared by embodiment 1-4 is modified
Film carries out salt rejection rate and water flux test, and test result is shown in Table 1.
The performance for the PVDF ultrafiltration membrane that the embodiment of table 1 and comparative example provide
Note：Salt rejection rate and water flux are all measured value during 2h after logical sewage, and each concentration of metal ions is 0.5mol/L
From the test result of table 1, PVDF ultrafiltration membrane that the embodiment 1-4 that is modified by surface is provided, and without place
The comparative example 1 of reason is compared, and water flux is slightly decreased, but salt rejection rate (resistance metal ion performance) is minimum to improve 6 times, and film wire resists
Pollutant performance significantly improves.
Claims (10)
1. a kind of polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method, including：
1) pvdf membrane surface is made to form C=C double bonds PVDF ultrafiltration membrane progress alkali process；
2) the pvdf membrane progress negative electrical charge with C=C double bonds is handled to obtain and carries SO3 -The PVDF ultrafiltration membrane of ion；
3) SO will be carried3 -The pvdf membrane of ion carries out sulphur aminating reaction and obtains the PVDF ultrafiltration membrane of surface modification.
2. polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 1, it is characterised in that described in step 1)
Alkali process is in NaOH and KMnO4Mixed aqueous solution in carry out, the mass fraction of mixed aqueous solution is 36%.
3. polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 2, it is characterised in that the NaOH and
KMnO4Mass ratio be 8:1.
4. polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 1, it is characterised in that described in step 2)
Negative electrical charge processing is in NaHSO3And H2SO4Mixed aqueous solution progress, the mass fraction of mixed aqueous solution is 4%.
5. polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 4, it is characterised in that the NaHSO3With
H2SO4Mass ratio be 1:1.
6. polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 1, it is characterised in that described in step 3)
Sulphur aminating reaction is in polyamino polymer and SOCl2Mixed aqueous solution in carry out, the mass fraction of mixed aqueous solution is
36%.
7. polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 6, it is characterised in that the polyamino gathers
Compound and SOCl2Mass ratio be 1:1.
8. polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 1, it is characterised in that described in step 3)
The pH value of sulphur aminating reaction is 6.0-8.5.
9. polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 1, it is characterised in that described in step 3)
Sulphur aminating reaction is carried out at room temperature, reaction time 60-300min.
10. the polyvinylidene fluoride (PVDF) ultrafiltration membrane surface modifying method according to claim 6 or 7, it is characterised in that more ammonia
Based polyalcohol is selected from poly- (N- (N- (2- amino-ethyls) -2- amino-ethyls) aspartic acid), polylysine, poly- (2- amino second
Methyl acrylate), the one or more in poly arginine.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113957610A (en) * | 2021-11-25 | 2022-01-21 | 北京化工大学 | Preparation and application of electrospun nanofiber oil-water separation membrane for water quality alkyl mercury detection |
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| CN113957610A (en) * | 2021-11-25 | 2022-01-21 | 北京化工大学 | Preparation and application of electrospun nanofiber oil-water separation membrane for water quality alkyl mercury detection |
| CN113957610B (en) * | 2021-11-25 | 2023-11-10 | 北京化工大学 | Method for high-precision separation of water quality alkyl mercury by using electrospun nanofiber oil-water separation membrane |
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