CN109433027A - A kind of hydrophilic antipollution ultrafiltration membrane and preparation method thereof - Google Patents
A kind of hydrophilic antipollution ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN109433027A CN109433027A CN201811564173.0A CN201811564173A CN109433027A CN 109433027 A CN109433027 A CN 109433027A CN 201811564173 A CN201811564173 A CN 201811564173A CN 109433027 A CN109433027 A CN 109433027A
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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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The present invention provides a kind of hydrophilic antipollution ultrafiltration membrane and preparation method thereof, belongs to functional polymer technology field of membrane materials.Under nitrogen protection, PVDF is dissolved in solvent for this method, and initiator, butyl bromide, methyl methacrylate and polyvinylpyrrolidone reaction, standing and defoaming is then added and obtains casting solution；Dehydrated alcohol and deionized water are uniformly mixed, coagulating bath is obtained；Obtained casting solution is toppled over and spreads to the uniform liquid film of thickness on a glass, is stopped in air, film-forming in coagulating bath is put into, falls off from glass plate to film, is taken out from coagulating bath, hydrophilic antipollution ultrafiltration membrane is obtained after flushing.Ultrafiltration membrane hydrophily of the invention and resistance tocrocking are excellent.
Description
Technical field
The invention belongs to functional polymer technology field of membrane materials, and in particular to a kind of hydrophilic antipollution ultrafiltration membrane and its
Preparation method.
Background technique
The advantages that excellent mechanical performance of Kynoar (PVDF) film, chemical stability and thermal stability, makes it extensively
Applied to UF membrane field.However the low interfacial tension of PVDF itself and hydrophobicity, easily adhere to the pollutants such as protein
Film surface or fenestra, cause fouling membrane, lead to flux depression, and separating property is deteriorated, and membrane lifetime shortens and separation costs increase.
Have a large amount of document and patent report at present, improves it in sewage treatment by carrying out hydrophilic modifying to PVDF
In application, main method of modifying being and not being machine particle blending, surface grafting, surface coating, the methods of chemical surface treatment.?
During immersion precipitation inversion of phases is film-made, membrane formation mechanism is closely related with membrance casting condition.The film tool of different membrance casting condition preparations
There are different membrane structure and film properties.Numerous scientific research scholars enter in-depth study to film forming procedure and membrane formation mechanism, wherein
Concentration, coagulation bath temperature, coagulation bath composition of polymer etc. are many principal elements for influencing film forming procedure.Xu et al. (Xu J,
Tang Y Wang Y et a1.Jou.Mem.Sci, 2014,455:121-130.) coagulation bath condition is had studied to polysulfones/class
The influence of capsaicine blend film pattern and performance, as a result, it has been found that with the increase of ethyl alcohol, glacial acetic acid content in coagulating bath, film surface
Copolymer level increases, and blend film surface hydrophilicity and resistance tocrocking improve.Jin Jian et al. (Zhang W, Zhu Y Liu X, et
2014,53 (3): a1.Ang.Che.Int.Edi 856-860.) prepares water-oil separating PAA- using Salt treatment phase inversion
G-PVDF film.The experimental results showed that film surface forms different size nanoscale PAA-gPVDF- microballoon, it is super close to assign film surface
Water/superoleophobic performance.Therefore, regulate and control the special construction that film forming procedure is needed by changing coagulation bath composition, it is right
It is had a very important significance in the film for preparing antifouling property.
During submerging inversion of phases, solvent and non-solvent carry out double diffusion, can change by adjusting coagulation bath composition
System thermodynamics split-phase rate forms different membrane structures into face, assigns film special performance.Therefore, by adjusting coagulating bath
Composition is a kind of simple, efficient method for improving porous film properties.
Summary of the invention
The contents of the present invention and are mentioned to solve the problems, such as that existing pvdf membrane surface strong-hydrophobicity and resistance tocrocking are poor
For a kind of hydrophilic antipollution ultrafiltration membrane and preparation method thereof.
Present invention firstly provides a kind of preparation methods of hydrophilic antipollution ultrafiltration membrane, this method comprises:
Step 1: under nitrogen protection, PVDF being dissolved in solvent, and initiator, butyl bromide, metering system is then added
Sour methyl esters and polyvinylpyrrolidone reaction, standing and defoaming obtain casting solution；
Step 2: dehydrated alcohol and deionized water are uniformly mixed, and obtain coagulating bath；The dehydrated alcohol and deionization
The mass ratio of water is (15-60): (40-85)；
Step 3: obtained casting solution is toppled over and spreads to the uniform liquid film of thickness on a glass, is stopped in air
Afterwards, it is put into film-forming in the coagulating bath of step 2, is fallen off from glass plate to film, is taken out from coagulating bath, obtained after flushing
Hydrophilic antipollution ultrafiltration membrane.
Preferably, the solvent of the step 1 is dimethylformamide, dimethyl acetamide or N-Methyl pyrrolidone.
Preferably, the initiator of the step 1 is azodiisobutyronitrile.
Preferably, the reaction temperature of the step 1 be 60~80 DEG C, the reaction time be 6~10h, revolving speed be 180~
240rpm。
Preferably, the standing and defoaming time of the step 1 is 12-24h.
Preferably, in the step 1 PVDF, butyl bromide, methyl methacrylate and polyvinylpyrrolidone matter
Amount is than being 45:1:4:1.
Preferably, the butyl bromide is bromination 1- butyl -3- vinyl imidazole.
Preferably, residence time is 10~30s to the step 3 in air.
The present invention also provides the hydrophilic antipollution ultrafiltration membranes that above-mentioned preparation method obtains.
Beneficial effects of the present invention
The present invention provides a kind of hydrophilic antipollution ultrafiltration membrane and preparation method thereof, the ultrafiltration membrane be by by PVDF with
The reaction of MMA-co-ILs copolymer hydrophilic additive, is prepared into hydrophilic composite film, and this method is the side using in-situ polymerization
Hydrophilic additive is combined on PVDF matrix by formula, increases its hydrophily, can by the composition of coagulating bath and the regulation of content
With the balance between Effective Regulation ultrafiltration membrane permeance property and antifouling property, to improve the hydrophily and anti-pollution of pvdf membrane
Metachromia.It is preparation method simple process of the invention, easily controllable.
Detailed description of the invention
Fig. 1 is the pure water flux figure of film obtained by comparative example 1 and embodiment 1-4.
Fig. 2 is film obtained by comparative example 1 and embodiment 1-4 to protein retention effect picture.
Fig. 3 is rejection effect figure of the film obtained by comparative example 1 and embodiment 1-4 to orange G dyestuff.
Fig. 4 is rejection effect figure of the film obtained by comparative example 1 and embodiment 1-4 to rhodamine 6G dyestuff.
Fig. 5 is flux recovery rate effect picture of the film obtained by comparative example 1 and embodiment 1-4 to orange G dyestuff.
Fig. 6 is flux recovery rate effect picture of the film obtained by comparative example 1 and embodiment 1-4 to rhodamine 6G dyestuff.
Specific embodiment
Present invention firstly provides a kind of preparation methods of hydrophilic antipollution ultrafiltration membrane, this method comprises:
Step 1: under nitrogen protection, PVDF being dissolved in solvent, and initiator, butyl bromide, metering system is then added
Sour methyl esters and polyvinylpyrrolidone reaction, standing and defoaming obtain casting solution；The solvent be preferably dimethylformamide,
Dimethyl acetamide or N-Methyl pyrrolidone；Initiator is preferably azodiisobutyronitrile；Butyl bromide is preferably bromination 1- fourth
Base -3- vinyl imidazole, the reaction temperature are preferably 60~80 DEG C, and the reaction time is preferably 10~14h, and revolving speed is preferably
180~240rpm, standing and defoaming temperature are preferably 40 DEG C, and the time is not particularly limited, and reach bubble-free in casting solution, excellent
It is selected as 12-24h, the PVDF, initiator, butyl bromide, the mass ratio of methyl methacrylate and polyvinylpyrrolidone are excellent
It is selected as 45:0.05:1:4:1.
Step 2: dehydrated alcohol and deionized water are uniformly mixed, and obtain coagulating bath；The dehydrated alcohol and deionization
The mass ratio of water is (15-60): (40-85)；The present invention regulates and controls the hydrophily of ultrafiltration membrane by controlling the proportionate relationship of ethyl alcohol
And resistance tocrocking, since the exchange rate of solvent and non-solvent becomes faster, occurs instantaneous demixing, can lead when ethanol content is too low
Cause forms big finger-like pore to which cutoff performance declines, when ethanol content is excessively high, due to the exchange rate of solvent and non-solvent
It is slack-off, occur delayed demixing, rate of film build reduce, the ethyl alcohol of high concentration make film formed finger-like pore change to spongy hole and
The thickness of film is thinning to will lead to film average pore size and porosity becomes larger to which hydrophily reduces, antifouling property decline.
Step 3: obtained casting solution is toppled over and spreads to the uniform liquid film of thickness, the thickness of the liquid film on a glass
Degree is preferably 0.2mm, in air it is preferred stop 10~30s after, film-forming in the coagulating bath of step 2 is put into, to film from glass
It falls off in glass plate, is taken out from coagulating bath, hydrophilic antipollution ultrafiltration membrane is obtained after flushing.
The present invention also provides the hydrophilic antipollution ultrafiltration membranes that above-mentioned preparation method obtains.
In order to make the objectives, technical solutions, and advantages of the present invention clearer, below in conjunction with attached drawing and specific implementation
Mode, the present invention will be described in further detail.It should be appreciated that the specific embodiments described herein are only to explain this
Invention, is not intended to limit the present invention.
Comparative example 1
PVDF powder is dried in vacuo for 24 hours at 80 DEG C, removes the moisture in raw material；Then, 45gPVDF is dissolved in
In 170gDMAc, heating stirring is made it dissolve at a temperature of 60 DEG C, temperature added after being increased to 80 DEG C 0.05gAIBN,
4gMMA, 1g ionic liquid bromination 1- butyl -3- vinyl imidazole, 1gPVP initiation reaction, sustained response 8h are homogeneous to get stablizing
Casting solution.By standing and defoaming 12h under the conditions of 40 DEG C of casting solution obtained.Casting solution is poured over to the glass of clean dried later
The liquid film with a thickness of 0.2mm is spread to scraper on plate, after stopping 30s in air, is put into 20 DEG C of deionized waters, is made uniform
Liquid film gradually split-phase, gel, solidification, film forming, and then be detached from from glass plate, obtain porous asymmetric pvdf membrane (being denoted as P0).
Embodiment 1
PVDF powder is dried in vacuo for 24 hours at 80 DEG C, removes the moisture in raw material；Then, 45gPVDF is dissolved in
In 170gDMAc, heating stirring is made it dissolve at a temperature of 60 DEG C, temperature added after being increased to 80 DEG C 0.05gAIBN,
4gMMA, 1g ionic liquid bromination 1- butyl -3- vinyl imidazole, 1gPVP initiation reaction, sustained response 8h are homogeneous to get stablizing
Casting solution.By standing and defoaming 12h under the conditions of 40 DEG C of casting solution obtained.Casting solution is poured over to the glass of clean dried later
The liquid film with a thickness of 0.2mm is spread to scraper on plate, after stopping 30s in air, is put into 20 DEG C of ethanol/waters by the matter of 15:85
It measures than preparing in the coagulating bath completed, makes uniform liquid film gradually split-phase, gel, solidification, film forming, and then take off from glass plate
From obtaining porous asymmetric PVDF composite membrane (being denoted as P15).
Embodiment 2
PVDF powder is dried in vacuo for 24 hours at 80 DEG C, removes the moisture in raw material；Then, 45gPVDF is dissolved in
In 170gDMAc, heating stirring is made it dissolve at a temperature of 60 DEG C, temperature added after being increased to 80 DEG C 0.05gAIBN,
4gMMA, 1g ionic liquid bromination 1- butyl -3- vinyl imidazole, 1gPVP initiation reaction, sustained response 8h are homogeneous to get stablizing
Casting solution.By standing and defoaming 12h under the conditions of 40 DEG C of casting solution obtained.Casting solution is poured over to the glass of clean dried later
The liquid film with a thickness of 0.2mm is spread to scraper on plate, after stopping 30s in air, is put into 20 DEG C of ethanol/waters by the matter of 30:70
It measures than preparing in the coagulating bath completed, makes uniform liquid film gradually split-phase, gel, solidification, film forming, and then take off from glass plate
From obtaining porous asymmetric PVDF composite membrane (being denoted as P30).
Embodiment 3
PVDF powder is dried in vacuo for 24 hours at 80 DEG C, removes the moisture in raw material；Then, 45gPVDF is dissolved in
In 170gDMAc, heating stirring is made it dissolve at a temperature of 60 DEG C, temperature added after being increased to 80 DEG C 0.05gAIBN,
4gMMA, 1g ionic liquid bromination 1- butyl -3- vinyl imidazole, 1gPVP initiation reaction, sustained response 8h are homogeneous to get stablizing
Casting solution.By standing and defoaming 12h under the conditions of 40 DEG C of casting solution obtained.Casting solution is poured over to the glass of clean dried later
The liquid film with a thickness of 0.2mm is spread to scraper on plate, after stopping 30s in air, is put into 20 DEG C of ethanol/waters by the matter of 45:55
It measures than preparing in the coagulating bath completed, makes uniform liquid film gradually split-phase, gel, solidification, film forming, and then take off from glass plate
From.Obtain porous asymmetric PVDF composite membrane (being denoted as P45).
Embodiment 4
PVDF powder is dried in vacuo for 24 hours at 80 DEG C, removes the moisture in raw material；Then, 45gPVDF is dissolved in
In 170gDMAc, heating stirring is made it dissolve at a temperature of 60 DEG C, temperature added after being increased to 80 DEG C 0.05gAIBN,
4gMMA, 1g ionic liquid bromination 1- butyl -3- vinyl imidazole, 1gPVP initiation reaction, sustained response 8h are homogeneous to get stablizing
Casting solution.By standing and defoaming 12h under the conditions of 40 DEG C of casting solution obtained.Casting solution is poured over to the glass of clean dried later
The liquid film with a thickness of 0.2mm is spread to scraper on plate, after stopping 30s in air, is put into 20 DEG C of ethanol/waters by the matter of 60:40
It measures than preparing in the coagulating bath completed, makes uniform liquid film gradually split-phase, gel, solidification, film forming, and then take off from glass plate
From.Obtain porous asymmetric PVDF composite membrane (being denoted as P60).
Characterization and performance test are carried out to membrane sample obtained below.
1, contact angle test: the contact angle using contact angle tester test water on pvdf membrane surface.Experimental result such as table 1
Table 1
| Embodiment | Comparative example 1 | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Contact angle (°) | 85 | 72 | 64 | 47 | 52 |
As it can be seen from table 1 film P0 contact angle obtained by comparative example 1 is 80-90 °, the composite membrane after ethanol bath
P15, P30, P45, P60 contact angle are remarkably decreased 40-50 ° than film P0, and with the increase of ethanol content in coagulating bath, contact angle
It is smaller, but when ethanol content is 60% in coagulating bath, film contact angle is increased slightly, and illustrating that film hydrophily reduces proves to bathe through alcohol
Caudacoria hydrophily is good, but ethanol content is unsuitable excessively high.
2, pure water flux is tested: cup type filter device is used, to sample film precompressed 10min, stream under the pressure of 0.1MPa
Amount is tested after stablizing, and water flux calculation formula is as follows:
JW=VW/A×t
JwFor pure water flux (L/h ﹒ m2)；VwFor the volume (L) through pure water；A is the effective area (m of ultrafiltration membrane2)；T is
Through the time (h).After tested, as shown in Figure 1, it can be seen that the pvdf membrane flux by alcohol bath increases, and as ethyl alcohol contains
The increase of amount, flux significantly increase.When ethanol content is 60wt%, flux reaches maximum value 718.6L/m2/ h, water pass through resistance
Power reduces.This is because film is easily formed more aperture, and hymeniderm layer is thinning after ethyl alcohol is added in coagulating bath, porosity increases
Add, average pore size increases, and flux increases.
3, rejection is tested: configuring bovine serum albumin(BSA) (BSA) aqueous solution of 0.1g/L, the rhodamine 6G and orange of 10mg/L
Yellow G aqueous solution, by pollutant by composite membrane, is measured with ultraviolet specrophotometer in 278.6nm wave under conditions of 0.1MPa
Absorbance under long.Rejection calculation formula is as follows:
R=(1-CP/C0) × 100%
R is the rejection (%) of film；CpFor the concentration (mg/mL) of solute in permeate；C0For the concentration of solute in feeding liquid
(mg/mL).After tested, composite membrane is illustrated in figure 2 to the retention situation of bovine serum albumin(BSA) (BSA).It can be seen that passing through alcohol
The pvdf membrane of bath can efficiently retain BSA, and with the increase of ethanol content, the rejection of composite membrane is higher while pure
Water flux also maintains higher level.Fig. 3 is rejection of the composite membrane to orange G.When ethanol content is 30wt%, rejection effect
Preferably, it can reach 95.3%.This is because due to the addition of ethyl alcohol, the phase rate of departure is caused to postpone, formd finer and close small
Hole, so that composite membrane be enable to play preferable separating effect.Fig. 4 is rejection of the composite membrane to rhodamine 6G.With coagulating bath
The rejection effect of the increase of middle ethanol content, composite membrane obviously improves, it may be said that bright composite membrane divides different pollutants are handled
It is all remarkably reinforced from efficiency.
4, flux recovery rate is tested: filtration of demineralized water is first passed through by pvdf membrane, filters BSA, rhodamine 6G, orange G later,
Refilter pure water.Calculation formula is as follows:
FRR=JR/JW× 100%
JRRestore flux (L/h ﹒ m for pure water2).After tested, as Fig. 5 Fig. 6 show composite membrane to orange G (Fig. 5) He Luodan
The flux of bright 6G (Fig. 6) and after being cleaned with pure water, the water flux recovery situation of composite membrane, it can be seen from the figure that composite membrane pair
The flux ratio pure water flux of dyestuff slightly reduces, but still keeps higher level.Secondly, composite membrane is after simple cleaning, flux
Recovery rate is at a normal level, and illustrates the pvdf membrane by alcohol bath, and flux recovery rate is still maintained at higher level, reaches as high as
100%, to improve the antifouling property of composite membrane.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (9)
1. a kind of preparation method of hydrophilic antipollution ultrafiltration membrane, which is characterized in that this method comprises:
Step 1: under nitrogen protection, PVDF being dissolved in solvent, and initiator, butyl bromide, methyl methacrylate is then added
Ester and polyvinylpyrrolidone reaction, standing and defoaming obtain casting solution；
Step 2: dehydrated alcohol and deionized water are uniformly mixed, and obtain coagulating bath；The dehydrated alcohol and deionized water
Mass ratio is (15-60): (40-85)；
Step 3: obtained casting solution being toppled over and spreads to the uniform liquid film of thickness on a glass, after stopping in air, is put
Enter film-forming in the coagulating bath of step 2, falls off from glass plate to film, taken out from coagulating bath, hydrophilic is obtained after flushing
Antipollution ultrafiltration membrane.
2. a kind of preparation method of hydrophilic antipollution ultrafiltration membrane according to claim 1, which is characterized in that the step
One solvent is dimethylformamide, dimethyl acetamide or N-Methyl pyrrolidone.
3. a kind of preparation method of hydrophilic antipollution ultrafiltration membrane according to claim 1, which is characterized in that the step
One initiator is azodiisobutyronitrile.
4. a kind of preparation method of hydrophilic antipollution ultrafiltration membrane according to claim 1, which is characterized in that the step
One reaction temperature is 60~80 DEG C, and the reaction time is 6~10h, and revolving speed is 180~240rpm.
5. a kind of preparation method of hydrophilic antipollution ultrafiltration membrane according to claim 1, which is characterized in that the step
One standing and defoaming time is 12-24h.
6. a kind of preparation method of hydrophilic antipollution ultrafiltration membrane according to claim 1, which is characterized in that the step
PVDF in one, butyl bromide, methyl methacrylate and polyvinylpyrrolidone mass ratio be 45:1:4:1.
7. a kind of preparation method of hydrophilic antipollution ultrafiltration membrane according to claim 1, which is characterized in that the fourth
Bromide salt is bromination 1- butyl -3- vinyl imidazole.
8. a kind of preparation method of hydrophilic antipollution ultrafiltration membrane according to claim 1, which is characterized in that the step
Three in air residence time be 10~30s.
9. the hydrophilic antipollution ultrafiltration membrane that preparation method described in claim 1-8 any one obtains.
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Cited By (3)
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| CN112755803A (en) * | 2019-10-21 | 2021-05-07 | 中国石油化工股份有限公司 | Method for preparing high-performance oil-water separation membrane |
| CN113652302A (en) * | 2021-09-01 | 2021-11-16 | 安徽山美生物科技有限公司 | Method for preparing skin care tea seed oil by separating unsaturated fatty acid from oil tea seed oil |
| US11623183B2 (en) * | 2020-05-07 | 2023-04-11 | Tiangong University | Synthesis of imidazolium-based functional ionic liquid copolymer and preparation method of alloy ultra-filtration membrane |
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| CN113652302B (en) * | 2021-09-01 | 2023-11-24 | 安徽山美生物科技有限公司 | Method for preparing skin-care tea seed oil by separating unsaturated fatty acid from tea seed oil |
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Application publication date: 20190308 |