CN105597576A - Preparation method of beta-cyclodextrin grafted polyvinylidene fluoride ultrafiltration membrane - Google Patents
Preparation method of beta-cyclodextrin grafted polyvinylidene fluoride ultrafiltration membrane Download PDFInfo
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- CN105597576A CN105597576A CN201510998116.3A CN201510998116A CN105597576A CN 105597576 A CN105597576 A CN 105597576A CN 201510998116 A CN201510998116 A CN 201510998116A CN 105597576 A CN105597576 A CN 105597576A
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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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
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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
- B01D67/0013—Casting processes
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
-
- 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
-
- 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
- B01D71/74—Natural macromolecular material or derivatives thereof
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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
- B01D2323/02—Hydrophilization
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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
- B01D2323/38—Graft polymerization
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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 invention discloses a preparation method of a beta-cyclodextrin grafted polyvinylidene fluoride ultrafiltration membrane. The preparation method comprises the following steps: preparing a polyvinylidene fluoride membrane and hydroxylating the polyvinylidene fluoride membrane to obtain a modified hydroxylated PVDF membrane; immersing the modified hydroxylated PVDF membrane with a trimesoyl chloride/n-hexane oil solution and a eta-cyclodextrin solution respectively to obtain the beta-cyclodextrin grafted polyvinylidene fluoride ultrafiltration membrane. The method disclosed by the invention is simple and feasible; the anti-pollution property of the PVDF membrane is improved; a traditional method of grafting by using plasmas and irradiation is avoided, so that equipment cost in actual production is reduced.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of grafted by beta cyclodextrinThe preparation method of polyvinylidene fluoride (PVDF) ultrafiltration membrane.
Background technology
In recent years, deepening continuously and the continuous expansion of application market along with membrane separation technique researchGreatly, membrane separation technique has become an important force of water treatment field. Can hold back according to filmThe difference of particle size, membrane for water treatment can be divided into micro-filtration membrane, milipore filter, NF membrane and reverse osmosisPermeable membrane. Micro-filtration membrane can be removed micron and other colloidal solid of submicron order, as general markStandard, micro-filtration membrane can be filtered the particle that is low to moderate 0.1 μ m. The aperture of milipore filter is generally at 5nmBetween 100nm, can 100% except the bacterium in anhydrating and virus etc. NF membrane andReverse osmosis membrane, can be except impurity such as the metal ions in anhydrating for less particle size range.
Kynoar due to have that mechanical strength is high, radioresistance good and chemically stable good etc. excellentPoint and be widely used in the preparation of membrane for water treatment. But because Kynoar is a kind of hydrophobicityPolymer, the film hydrophily of preparing is poor. Under higher pressure, water can be mandatoryGround is by hydrophobic polyvinylidene fluoride film, but in this case, polyvinylidene fluoride film is logicalIt is evenly wetting that Chang Buhui becomes, and therefore polyvinylidene fluoride film has very low water flux conventionally, fallsLow production efficiency, and under higher operating pressure, PVDF membrane pore-structure is likelyDestroyed, reduced the service life of polyvinylidene fluoride film. Thereupon occur problem be byIn the hydrophobicity of material, also all present stronger hydrophobicity with PVDF film formation surface processed,In actual use, because separated material easily produces the reasons such as absorption at hydrophobic surface, cause filmPollute. Make milipore filter itself there is antifouling property, be solve that film pollutes the most effectively and rootOne of this method.
Summary of the invention
The object of the present invention is to provide a kind of grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membranePreparation method, by pvdf membrane surface grafting beta-schardinger dextrin-, improves its hydrophily and anti-Pollutant performance, avoids using the conventional method of plasma, irradiation grafting, is reduced in actual lifeEquipment cost in product.
The present invention is specifically achieved through the following technical solutions:
A preparation method for grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane, comprises following stepRapid:
1) preparation of polyvinylidene fluoride film
Kynoar and polyvinylpyrrolidone are dissolved in DMA to be castFilm liquid, is placed in vacuum drying chamber vacuum defoamation by the casting solution mixing and processes 12 hours,Deaeration is poured on this casting solution on glass plate after processing, and scrapes and makes with the scraper of 200 μ mFilm then leaves standstill and it is soaked in pure water 48 hours after 30 seconds in air, makes partially poly-Fluoride film;
2) preparation of hydroxylating polyvinylidene fluoride film
Polyvinylidene fluoride film is wetting by alcohol immersion, and water displacement ethanol 30 minutes, makes filmIn hole, be full of water, then be immersed in the KOH/KMnO of 80 DEG C4In solution 5 minutes, then willPolyvinylidene fluoride film is transferred to containing NaHSO3/H2SO4In solution 30 minutes, poly-after modificationThe hydroxylated pvdf membrane that vinylidene fluoride film obtains with deionized water rinsing;
3) preparation of the polyvinylidene fluoride film of grafted by beta cyclodextrin
Hydroxylated polyvinylidene fluoride film is immersed in to 50ml pyromellitic trimethylsilyl chloride/n-hexaneIn (0.6%, w/v) lysigenous oil solution after 30 minutes, then to be soaked in pH value be 9 βIn-cyclodextrin solution 90 minutes, modified polyvinilidene fluoride film is rinsed repeatedly by deionized water,Obtain the polyvinylidene fluoride film of the grafted by beta cyclodextrin of modification.
Kynoar of the present invention and polyvinylpyrrolidone are respectively casting solution gross weight18% and 4% of amount.
KOH/KMnO of the present invention4In solution, the concentration of KOH is 3M, KMnO4Mass concentration be 4%.
NaHSO of the present invention3/H2SO4NaHSO in solution3And H2SO4Quality denseDegree is 5%.
In n-hexane oil solution of the present invention, the mass concentration of pyromellitic trimethylsilyl chloride is 6g/L.
In beta-schardinger dextrin-solution of the present invention, contain NaOH and Na2CO3, describedNaOH and Na2CO3Mass ratio be 1:2, the mass concentration of described beta-schardinger dextrin-is18g/L。
Beneficial effect of the present invention is: the PVDF that the present invention adopts grafted by beta cyclodextrin not onlyThere is higher hydrophily, and in the pollution experiment of film, demonstrate higher resistance tocrocking;Use a kind of simple chemical modification method, improved the resistance tocrocking of pvdf membrane, keep awayExempt to use the conventional method of plasma, irradiation grafting, the equipment being reduced in actual production becomesThis.
Brief description of the drawings
Fig. 1 is infrared spectrum (upper curve) and the original PVDF of modification pvdf membrane of the present inventionThe infrared spectrum (lower curve) of film.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and the following stated is only to thisThe preferred embodiment of invention, not does other forms of restriction to the present invention, any familiarProfessional and technical personnel may utilize the technology contents of above-mentioned announcement to be changed to equal changeThe equivalent embodiment changing. Every the present invention program's content that do not depart from, real according to technology of the present inventionAny simple modification or equivalent variations that confrontation following examples are done, all drop on guarantor of the present inventionProtect in scope.
The preparation of embodiment 1 grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane
A kind of grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane, specifically preparation by the following methodComplete:
The preparation of pvdf membrane: PVDF22.5g (18wt%) and PVP5g (4wt%) are dissolved inIn DMAc97.5g, this casting solution is stirred 8 hours in 60 DEG C, then will mixCasting solution be placed in vacuum drying chamber vacuum defoamation process 12 hours, deaeration process after, willThis casting solution is poured on glass plate, by the scraper striking film forming of 200 μ m, then at airIn leave standstill after 30 seconds, it is soaked in pure water 48 hours, make pvdf membrane;
The preparation of β-CD-PVDF film: pvdf membrane is wetting by alcohol immersion, water displacementEthanol 30 minutes, makes to be full of in fenestra water. Be immersed in again the 3MKOH/4%K of 80 DEG CMnO4In solution 5 minutes, then pvdf membrane is transferred to containing 5%NaHSO3/5％H2SO4In solution 30 minutes, the hydroxyl that the polyvinylidene fluoride film after modification obtains with deionized water rinsingThe pvdf membrane of base. Again film is immersed in to 50mlTMC/ n-hexane (0.6%, w/v) and dissolves shapeBecome oil solution in 30 minutes. And then pvdf membrane is immersed in to pH is adjusted to 9 NaOH and Na2CO3Mixing quality is than being in β-CD (1.8%, w/v) solution of 1:2 90 pointsClock. Finally, modification pvdf membrane is rinsed repeatedly by deionized water. Obtain the β of modification-CD-PVDF film.
Embodiment 2
For β-CD-PVDF film prepared by embodiment 1 carries out chemical structure analysis, use BRukerTENSOR27 infrared spectrum analyser has carried out structural characterization.
As can be seen from Figure 1: 1405cm-1And 1168cm-1Characteristic absorption peak be CH2andCF2Stretching vibration peak, C-C skeletal vibration is at 877cm-1, derive from the carbonyl (C=O) of PVPFlexural vibrations at 1670cm-1. With respect to original pvdf membrane, modification pvdf membrane (onCurve: β-CD-PVDF) in there is a series of new absworption peak, 3200 to 3600cm-1Wide and strong absworption peak represents to come from the hydroxyl (– OH of cyclodextrin) absworption peak, C-O-CStretching vibration peak at 1240cm-1And 1040cm-1Be observed. These all represent β-ring pasteEssence (β-CD) has been grafted to the surface of PVDF by the link of TMC.
Embodiment 3
Measure the contact angle of film by using contact angle measurement. This experiment is the temperature of 25 DEG CUnder degree, 2 μ L pure water are dropped in to the surface of film, measure the contact angle of water on film surface.
Choose five zoness of different of every film and measure, finally connecing to this film of averagedFeeler size, embodiment 1 prepares gained β-CD-PVDF film contact angle by former film after tested85.9 ° are reduced to 48.5 °, and its hydrophily is largely increased.
Embodiment 4
The antifouling property of film is using bovine serum albumin (BSA) solution of 0.1g/L as model eggIn vain, evaluate by circulating filtration. First the operating pressure at 0.1MPa by BSA solutionUnder, use membrane filtration 30 minutes, and its flux is designated as to Jp. Stand-by pure water rinses 30 repeatedlyAfter minute, use membrane filtration pure water 30 minutes, and keep the operating pressure of its 0.1MPa, gainedTo flux be designated as Jr. This experiment loops twice. Flux recovery rate (FRR) is calculated publicFormula is as follows:
In the period 1, the pure water flux of original pvdf membrane only returns to 40% of initial flux(FRR), and the water flux of embodiment 1 β-CD-PVDF film returns to 47.4% (FRR),In the circulating filtration of second round, the FRR of β-CD-PVDF film is 49.1%, also obviousHigher than the FRR (31%) of original pvdf membrane.
Embodiment 5
The permeation flux of film is measured by Ultrafiltration experiment device. Experiment is carried out under 0.1MPa.First by film precompression 30 minutes under pure water, record data after its flux stabilized. After testedThe flux of original membrane only has 132.2 (L/m2, and the flux of β-CD-PVDF film rises to 7 h)66.5(L/m2h)。
The water absorption rate test process of film is as follows, before testing, all films is positioned over to 5In the baking oven of 0 DEG C, dry 1 hour, measure its dry weight. Then at room temperature, all films are soakedBubble in pure water 24 hours. Measuring before its weight in wet base, first use filter paper to remove striping remained on surfaceMoisture. Water absorption rate (η) computing formula is as follows:
Wherein, mwetAnd mdryRepresent respectively its weight in wet base and dry weight.
The water absorption rate of original membrane is the water suction of 17.1%, embodiment β-CD-PVDF film after testedRate is 55.6%, and result proves that its hydrophily is improved.
Claims (6)
1. a preparation method for grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane, its feature existsIn comprising the following steps:
1) preparation of polyvinylidene fluoride film
Kynoar and polyvinylpyrrolidone are dissolved in DMA and are obtainedCasting solution, is placed in vacuum drying chamber vacuum defoamation by the casting solution mixing and processes 12hAfter, masking on glass plate is soaked it 48h after standing 30s in air, system in pure waterObtain polyvinylidene fluoride film;
2) preparation of hydroxylating polyvinylidene fluoride film
Polyvinylidene fluoride film is wetting by alcohol immersion, and water displacement ethanol makes to be full of in fenestraWater, then be immersed in the KOH/KMnO of 80 DEG C45min in solution, then by KynoarFilm is transferred to containing NaHSO3/H2SO430min in solution, the polyvinylidene fluoride film after modification is usedThe hydroxylated pvdf membrane that deionized water rinsing obtains;
3) preparation of the polyvinylidene fluoride film of grafted by beta cyclodextrin
Hydroxylated polyvinylidene fluoride film is immersed in to the n-hexane oil solution of pyromellitic trimethylsilyl chlorideAfter middle 30min, then to be soaked in pH value be 90min in 9 beta-schardinger dextrin-solution, by modificationPolyvinylidene fluoride film rinses repeatedly by deionized water, has obtained the grafted by beta cyclodextrin of modificationPolyvinylidene fluoride film.
2. a kind of grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane according to claim 1Preparation method, it is characterized in that: described Kynoar and polyvinylpyrrolidone are respectivelyFor 18% and 4% of casting solution gross weight.
3. a kind of grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane according to claim 1Preparation method, it is characterized in that: described KOH/KMnO4The concentration of KOH in solutionFor 3M, KMnO4Mass concentration be 4%.
4. a kind of grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane according to claim 1Preparation method, it is characterized in that: described NaHSO3/H2SO4NaHSO in solution3WithH2SO4Mass concentration be 5%.
5. a kind of grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane according to claim 1Preparation method, it is characterized in that: the matter of pyromellitic trimethylsilyl chloride in described n-hexane oil solutionAmount concentration is 6g/L.
6. a kind of grafted by beta cyclodextrin polyvinylidene fluoride (PVDF) ultrafiltration membrane according to claim 1Preparation method, it is characterized in that: in described beta-schardinger dextrin-solution, contain NaOH and Na2CO3, described NaOH and Na2CO3Mass ratio be 1:2, described beta-schardinger dextrin-Mass concentration is 18g/L.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957089A (en) * | 2017-04-17 | 2017-07-18 | 同济大学 | A kind of twice-modified method of discarded reverse osmosis membrane available for treatment of dyeing wastewater |
| CN108031313A (en) * | 2017-12-23 | 2018-05-15 | 刘顶康 | A kind of strong antipollution ultrafiltration membrane of hydrophily |
| CN108126529A (en) * | 2018-01-29 | 2018-06-08 | 中铁建设集团有限公司 | A kind of filter membrane material for adhering to nanosponges sorbing material and preparation method thereof |
| CN108671901A (en) * | 2018-05-25 | 2018-10-19 | 北京师范大学 | A kind of water body removes the preparation method and application of caesium surface modified membrane |
| CN109364769A (en) * | 2018-11-02 | 2019-02-22 | 江苏大学 | The preparation method of pollution-resistant Enoxacin molecularly imprinted composite membrane material |
| CN109734228A (en) * | 2019-03-25 | 2019-05-10 | 新乡学院 | A kind of compound sewage processing method |
| CN110204823A (en) * | 2019-06-12 | 2019-09-06 | 金华市捷特包装有限公司 | A kind of high-performance rotational moulding case |
| CN113144921A (en) * | 2021-02-23 | 2021-07-23 | 西南石油大学 | Super-hydrophilic composite membrane suitable for oil-water separation in severe environment and preparation method thereof |
| CN113600037A (en) * | 2021-09-22 | 2021-11-05 | 天津工业大学 | Renewable PVDF (polyvinylidene fluoride) membrane with adsorption function and preparation method thereof |
| CN114307667A (en) * | 2021-12-01 | 2022-04-12 | 佛山市南海区苏科大环境研究院 | Water-soluble aldehyde-based cyclodextrin-polyethyleneimine coating modified polymer film and preparation method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106957089A (en) * | 2017-04-17 | 2017-07-18 | 同济大学 | A kind of twice-modified method of discarded reverse osmosis membrane available for treatment of dyeing wastewater |
| CN108031313A (en) * | 2017-12-23 | 2018-05-15 | 刘顶康 | A kind of strong antipollution ultrafiltration membrane of hydrophily |
| CN108126529A (en) * | 2018-01-29 | 2018-06-08 | 中铁建设集团有限公司 | A kind of filter membrane material for adhering to nanosponges sorbing material and preparation method thereof |
| CN108126529B (en) * | 2018-01-29 | 2020-12-15 | 中铁建设集团有限公司 | Filter membrane material attached with nano sponge adsorption material and preparation method thereof |
| CN108671901A (en) * | 2018-05-25 | 2018-10-19 | 北京师范大学 | A kind of water body removes the preparation method and application of caesium surface modified membrane |
| CN108671901B (en) * | 2018-05-25 | 2020-10-02 | 北京师范大学 | Preparation method and application of surface modified membrane for removing cesium in water body |
| CN109364769A (en) * | 2018-11-02 | 2019-02-22 | 江苏大学 | The preparation method of pollution-resistant Enoxacin molecularly imprinted composite membrane material |
| CN109734228B (en) * | 2019-03-25 | 2021-11-09 | 新乡学院 | Composite sewage treatment method |
| CN109734228A (en) * | 2019-03-25 | 2019-05-10 | 新乡学院 | A kind of compound sewage processing method |
| CN110204823A (en) * | 2019-06-12 | 2019-09-06 | 金华市捷特包装有限公司 | A kind of high-performance rotational moulding case |
| CN113144921A (en) * | 2021-02-23 | 2021-07-23 | 西南石油大学 | Super-hydrophilic composite membrane suitable for oil-water separation in severe environment and preparation method thereof |
| CN113600037A (en) * | 2021-09-22 | 2021-11-05 | 天津工业大学 | Renewable PVDF (polyvinylidene fluoride) membrane with adsorption function and preparation method thereof |
| CN114307667A (en) * | 2021-12-01 | 2022-04-12 | 佛山市南海区苏科大环境研究院 | Water-soluble aldehyde-based cyclodextrin-polyethyleneimine coating modified polymer film and preparation method thereof |
| CN114307667B (en) * | 2021-12-01 | 2024-03-15 | 苏州科技大学 | Water-soluble aldehyde cyclodextrin-polyethyleneimine coating modified polymer film and preparation method thereof |
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Application publication date: 20160525 |