CN111266023B - Polyvinyl imidazole functionalized polysulfone microfiltration membrane and preparation method and application thereof - Google Patents
Polyvinyl imidazole functionalized polysulfone microfiltration membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 143
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 55
- 238000001471 micro-filtration Methods 0.000 title claims abstract description 36
- 229920002006 poly(N-vinylimidazole) polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000001179 sorption measurement Methods 0.000 claims abstract description 26
- 150000001450 anions Chemical class 0.000 claims abstract description 23
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 claims abstract description 21
- 231100000331 toxic Toxicity 0.000 claims abstract description 15
- 230000002588 toxic effect Effects 0.000 claims abstract description 15
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- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 arsenate anions Chemical class 0.000 claims abstract description 11
- 238000010559 graft polymerization reaction Methods 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 4
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- 238000006243 chemical reaction Methods 0.000 claims description 8
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- 239000012153 distilled water Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
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- 238000002791 soaking Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical group C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
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- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
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- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 238000002798 spectrophotometry method Methods 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 150000003512 tertiary amines Chemical group 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 abstract description 11
- 150000002500 ions Chemical class 0.000 abstract description 7
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical compound [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 229940000489 arsenate Drugs 0.000 abstract description 4
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- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
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- 125000001302 tertiary amino group Chemical group 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- IYWCBYFJFZCCGV-UHFFFAOYSA-N formamide;hydrate Chemical compound O.NC=O IYWCBYFJFZCCGV-UHFFFAOYSA-N 0.000 description 4
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- 238000011282 treatment Methods 0.000 description 3
- 206010028980 Neoplasm Diseases 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
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- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-N Arsenic acid Chemical compound O[As](O)(O)=O DJHGAFSJWGLOIV-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 208000012902 Nervous system disease Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 125000000129 anionic group Chemical group 0.000 description 1
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- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
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- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 231100000003 human carcinogen Toxicity 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
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- 229910052761 rare earth metal Inorganic materials 0.000 description 1
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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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/103—Arsenic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention belongs to the technical field of polymer membrane materials, and provides a polyvinyl imidazole functionalized polysulfone micro-filtration membrane and a preparation method and application thereof in order to solve the problems of low ion filtering efficiency of a porous membrane to chromate and arsenate and the like at present, wherein the polysulfone membrane is used as a base membrane, and aromatic tertiary amine groups are bonded on the surface of the modified polysulfone membrane after chloromethylation; placing the membrane in a dimethylformamide solution containing a vinyl imidazole monomer and an oil-soluble initiator, and carrying out graft polymerization on the surface of the membrane under the action of a redox type surface initiation system consisting of tertiary aromatic amine and BPO or AIBN to obtain the polyvinyl imidazole functionalized polysulfone microfiltration membrane PSF-g-PVI. The preparation method is simple and easy to operate. Has strong adsorption effect on chromate and arsenate anions, and can be used as a filter membrane for membrane separation to effectively remove toxic anions. The polysulfone membrane is a microporous filter membrane, has high flux, and has excellent mechanical property, thermal stability, chemical stability and the like of the polysulfone membrane.
Description
Technical Field
The invention belongs to the technical field of polymer membrane materials, and particularly relates to a polyvinyl imidazole functionalized polysulfone microfiltration membrane, and a preparation method and application thereof, which are used for efficiently intercepting toxic anions in water.
Background
Chromates and arsenates are toxic anionic pollutants that can contaminate water systems, enter the food chain, and cause fatal human diseases. Hexavalent chromium (cr (vi)) is considered to be a highly toxic substance, and its chromate salts can cause cancer, mutation and teratogenicity after entering the human body. Arsenates containing pentavalent arsenic as (v) have been classified as class I human carcinogens, and arsenic exposure can lead to skin and various internal cancers as well as other diseases such as cardiovascular and nervous system diseases. Therefore, it is urgently required to develop a water treatment strategy to reduce the concentrations of chromic acid and arsenic acid in water to the allowable levels (allowable concentrations in drinking water are 0.05 mg/L and 10. mu.g/L, respectively) for drinking water and industrial wastewater. Various methods such as chemical precipitation, coagulation/flocculation, ion exchange, adsorption, biological process, etc. have been widely used for removing As (V) and Cr (VI) substances from water. However, these methods suffer from various drawbacks, such as the formation of toxic sludge and expensive operating costs. Although adsorption is a simple technique, most adsorbents have certain disadvantages, such as low adsorption affinity, poor recoverability, high operating and maintenance costs, etc.
At present, a pressure-driven membrane filtration method is used as a novel separation technology, and is widely applied to the treatment of industrial wastewater and the protection of water environment due to the modularized flexibility, limited space requirement, easiness in scale production and environmental protection. Although membrane separation techniques have been used to remove chromates and arsenates from water, conventional membrane separation techniques have certain limitations.
Three industrial membranes, namely a micro-filtration membrane, an ultrafiltration membrane and a nanofiltration membrane, have separation functions based on a sieving mechanism or a size exclusion effect, so that small molecular substances are difficult to reject or remove from an aquatic medium. Only those particles whose size is larger than the pore size of the membrane can be repelled and removed. Chromate (CrO)4 2-) And arsenate (AsO)4 3-) Has an ionic radius of 0.240 nm and 0.248 nm, respectively, and it is obvious that in order to remove them from water, the pore sizes of microfiltration membrane (pore size of 0.1-10 μm) and ultrafiltration membrane (1-100 nm) are not applicable, and the efficiency is too low, even if a nanofiltration membrane having a pore size of 1-2 nm is used, ions dissolved in water such as CrO4 2-And AsO4 3-It is difficult to completely remove it.
Therefore, in recent years, it has been attempted to functionalize the surface of a porous membrane by graft modification, and grafting macromolecules having an adsorption function to the surface of the porous membrane is a novel and very effective way to effectively remove dyes. However, graft polymerization on porous membranes has been difficult so far, and various radiation-induced polymerization methods including ultraviolet irradiation, radiation induction, electron beam treatment and low-temperature plasma treatment have been generally used, which are difficult to operate, complicated in equipment, high in cost, and the base membrane tends to be damaged to some extent during the implementation.
Disclosure of Invention
The invention aims to solve the problem that the existing porous membrane has chromate (CrO) on the chromate4 2-) And arsenate (AsO)4 3-) The preparation method is novel, simple in process and high in rejection capacity for toxic anions.
The chloromethylated polysulfone CMPSF used in the invention can be prepared according to the method described in the literature [ preparation of naphthoic acid functionalized polysulfone and fluorescence emission characteristics of complex with Eu (III) rare earth ion, Wang Ming Juan, Gao Bao jiao, Du Jun Mei, applied chemistry, 2013, 30(3): 283) -289], and has the film thickness of about 200 μm, the pore diameter of 0.1-1 μm and the chlorine content of 2 mmol/g.
The invention is realized by adopting the following technical scheme: a polyvinyl imidazole functionalized polysulfone microfiltration membrane is composed of a polysulfone base membrane PSF (composed of a compact skin layer and a macroporous support structure)) and polyvinyl imidazole PVI, and has a structure shown in formula (I):
。
the preparation method of the polyvinyl imidazole functionalized polysulfone microfiltration membrane comprises the steps of taking a polysulfone membrane PSF as a base membrane, modifying through chloromethylation, and bonding an aromatic tertiary amine group on the surface of the base membrane; and then placing the membrane in a dimethylformamide solution containing a vinyl imidazole monomer VI and an oil-soluble initiator, and carrying out graft polymerization on the membrane surface under the action of a redox type surface initiation system consisting of tertiary aromatic amine and BPO or AIBN to obtain the polyvinyl imidazole functionalized polysulfone microfiltration membrane PSF-g-PVI.
The method comprises the following specific steps:
(1) preparing a modified polysulfone membrane PSF-DEA with a side chain bonded with aromatic tertiary amine: adding 0.1g of chloromethylated polysulfone membrane CMPSF into 60mL of mixed solvent of ethanol, water and N, N-dimethylformamide, swelling for 2h, adding 0.13g of reaction reagent 3-hydroxy-N, N-diethylaniline HDEA, and adding 0.12-0.13g of acid-binding agent and N2Stirring at the constant temperature of 70-80 ℃ under protection for reaction for 6-8h, taking out the membrane, repeatedly washing with a mixed solution of ethanol and distilled water in a volume ratio of 1:1, and drying in vacuum to constant weight to obtain a modified polysulfone membrane PSF-DEA with a side chain bonded with aromatic tertiary amine;
(2) preparing a polyvinyl imidazole functionalized polysulfone microfiltration membrane: 0.1g of PSF-DEA membrane was added to 70mL of N, N-Dimethylformamide (DMF), allowed to swell for 2 to 3 hours, and Vinylimidazole (VI), N2And after bubbling for half an hour, heating to 60-70 ℃, adding an initiator, reacting for 10-12 hours, taking out the membrane, respectively soaking the membrane in DMF (dimethyl formamide), washing the grafted membrane with ethanol, and drying in vacuum to constant weight to obtain the polyvinyl imidazole functionalized polysulfone microfiltration membrane PSF-g-PVI.
In the mixed solvent of the ethanol, the water and the N, N-dimethylformamide in the step (1), the volume ratio of the ethanol to the water to the N, N-dimethylformamide is 1:1: 2; the acid-binding agent is Na2CO3、NaHCO3NaOH or triethylamine.
The dosage of the vinyl imidazole in the step (2) is 4.4-5% of the mass of the solution; the initiator is dibenzoyl peroxide (BPO) or Azobisisobutyronitrile (AIBN), and the dosage of the initiator is 1.4 percent of the mass of the vinyl imidazole.
The polyvinyl imidazole functionalized polysulfone microfiltration membrane is applied to adsorption and interception of toxic anions.
With CrO in an aqueous medium4 2-And AsO4 3-Two toxic anions are target removers, and the removal effect of the micro-filtration membrane PSF-g-PVI on the two target removers is measured by adopting an adsorption method and a permeation method.
The adsorption method specifically comprises the following steps: k with the preparation concentration of 10mmol/L2CrO4Or Na3AsO4Adjusting pH of the aqueous solution to 3 and 5, respectively, accurately measuring area of 0.02 g of imidazole-functionalized microfiltration membrane PSF-g-PVI, cutting into pieces, placing into 20mL of the aqueous solution, respectively, performing adsorption experiment at 25 deg.C in a water bath constant temperature oscillator, and measuring HCrO in the supernatant by spectrophotometry (lambda =540 nm) and ICP-AES method, respectively4 -And H2AsO4 -Toxic anion concentration (CrO at pH =34 2-With HCrO4 -The form exists; at pH =5, AsO4 3-With H2AsO4 -In the form) and the respective adsorption capacities were calculated.
The infiltration method comprises the following specific steps: k with the preparation concentration of 5mmol/L2CrO4Or Na3AsO4Adjusting the pH value of the aqueous solution to 3 and 5 respectively, sucking 80mL of 5mmol/L solution into a syringe, preparing a needle filter by taking a PSF-g-PVI membrane as a filter membrane, and connecting the filter membrane with the syringe; the solution is filtered by pushing the injector by hand, and the filter liquor is received by the container; the anion concentration in the filtrate was measured at different volume intervals and the respective removal rates were calculated.
The invention has the following beneficial effects:
1) designing and developing a polysulfone microfiltration membrane functionalized by polyvinyl imidazole and a preparation method thereof, namely, realizing grafting of the polyvinyl imidazole on the surface of the polysulfone microfiltration membrane by constructing a redox initiation system formed by a group on the surface of the membrane and an initiator in a solution, thereby realizing imidazole functionalization of the polysulfone microfiltration membrane. The method has the advantages of simple process, mild conditions and easy operation.
2) The prepared functional microporous filter membrane can keep high water flow, and the grafted imidazole group is protonated in acidic and neutral aqueous solutions and can generate strong electrostatic action on anions, so that toxic anions can be efficiently adsorbed to realize interception of the anions.
The grafted microporous filter membrane prepared by the method is HCrO4 -And H2AsO4 -The adsorption capacity of the ions can be respectively up to 11.8 mu mol/cm2And 7.2. mu. mol/cm2(ii) a Even if K2CrO4And Na3AsO4The concentration of the aqueous solution is up to 5mmol/L (in general, the concentration of both anions in water is less than 5 mmol/L), passing through 4cm2The functional microporous filter membrane PSF-g-PVI is within 0-60 ml, the retention rate of the functional membrane on the functional membrane is still higher than 95%, and the good removal efficiency is shown.
3) The preparation process of the invention takes the polysulfone membrane as the matrix membrane, thus having good chemical stability, thermal stability and mechanical property of the polysulfone membrane and being applicable to the requirement of industrial production. The invention has obvious reference value in the aspect of polymer functionalization of the membrane and has important scientific significance for water environment treatment.
In order to illustrate the chemical structure and the appearance of the polyvinyl imidazole functionalized polysulfone microfiltration membrane, the invention is further illustrated by combining the attached drawing.
Drawings
FIG. 1 shows the base membrane CMPSF (A) and the functional membrane PSF-g-scanning electron micrographs of cross sections of pvi (b); it can be seen from FIG. 1 (A) that it consists of a thin dense skin layer and a porous lower layer having a finger-like cavity and a macroporous structure, and the thickness of the membrane skin layer is greatly increased after graft polymerization (see FIG. 1 (B)) due to graft polymerization of monomeric vinylimidazole on the membrane surface. The surface layer of the PSF-g-PVI membrane consists of the original skin layer of the CMPSF membrane and the grafted layer of PVI, and is chemically bonded to the base membrane.
Fig. 2 is a self-made needle filter.
FIG. 3 is a PSF-g-PVI membrane pair HCrO4 -And H2AsO4 -Isothermal adsorption lines of ions.
FIG. 4 is HCrO4 -And H2AsO4 -Retention of ions as a function of permeate volume.
Detailed Description
The preparation method and application of the polyvinyl imidazole functionalized polysulfone microfiltration membrane are illustrated by the following examples.
Preparation of polyvinyl imidazole functionalized polysulfone microfiltration membrane
Example 1:
in a four-necked flask equipped with a stirrer, a condenser and a thermometer, 0.1g of CMPSF and 60mL of a mixed solvent composed of ethanol, water and DMF (volume ratio =1:1: 2) were charged, and after swelling for 2 hours, 0.13g of 3-hydroxy-N, N-diethylaniline (HDEA) and 0.12g of Na were added2CO3，N2Protecting, stirring at the constant temperature of 80 ℃ for reaction for 6 h, taking out the membrane, repeatedly washing by using a mixed solvent of ethanol and distilled water with the volume ratio of 1:1, and drying in vacuum to constant weight to obtain the modified polysulfone membrane PSF-DEA with the side chain bonded with the aromatic tertiary amine, wherein the bonding amount is 1.72 umol/cm2。
0.1g of PSF-DEA membrane was then added to 70mL of DMF and after swelling for 2 hours, 3.2 mL of the monomeric Vinylimidazole (VI), N2After bubbling for half an hour, heating to 70 ℃, adding 0.04 g of initiator, reacting for 10 hours, taking out the membrane, soaking the membrane in DMF and ethanol, repeatedly washing the grafted membrane, and drying in vacuum to constant weight to obtain the polysulfone microfiltration membrane (PSF-g-PVI) grafted with the polyvinyl imidazole, wherein the grafting degree of the polyvinyl imidazole is 0.25 mg/cm2. The resulting microfiltration membrane was electronically scanned, and the results are shown in FIG. 1.
Example 2:
in a four-necked flask equipped with a stirrer, a condenser and a thermometer, 0.1g of CMPSF and 60mL of a mixed solvent composed of ethanol, water and DMF (volume ratio =1:1: 2) were charged, and after swelling for 2 hours, 0.13g of 3-hydroxy-N, N-diethylaniline (HDEA) and 0.125g of NaHCO were added3，N2Protecting, stirring at the constant temperature of 70 ℃ for reaction for 7 h, taking out the membrane, repeatedly washing by using a mixed solvent of ethanol and distilled water with the volume ratio of 1:1, and drying in vacuum to constant weight to obtain the modified polysulfone membrane PSF-DEA with the side chain bonded with the aromatic tertiary amine, wherein the bonding amount is 1.64 umol/cm2。
0.1g of PSF-DEA membrane was then added to 70mL of DMF, and after swelling for 2.5 hours, 3.1 mL of the monomeric Vinylimidazole (VI), N2Bubbling for half an hour, heating to 70 ℃, adding 0.05 g of initiator, reacting for 11 hours, taking out the membrane, soaking in DMF and ethanol, andrepeatedly washing the grafted membrane, and vacuum drying to constant weight to obtain polysulfone membrane (PSF-g-PVI) grafted with polyvinyl imidazole with grafting degree of 0.20 mg/cm2。
Example 3:
0.1g of CMPSF and 60mL of a mixed solvent consisting of ethanol, water and DMF (volume ratio =1:1: 2) were put into a four-necked flask equipped with a stirrer, a condenser tube and a thermometer, and after swelling for 2 hours, 0.13g of 3-hydroxy-N, N-diethylaniline (HDEA) and 0.12g of NaOH, N-diethylaniline were added2Protecting, stirring at the constant temperature of 70 ℃ for reaction for 6 h, taking out the membrane, repeatedly washing by using a mixed solvent of ethanol and distilled water with the volume ratio of 1:1, and drying in vacuum to constant weight to obtain the modified polysulfone membrane PSF-DEA with the side chain bonded with the aromatic tertiary amine, wherein the bonding amount is 1.67 umol/cm2。
0.1g of PSF-DEA membrane was then added to 70mL of DMF and after swelling for 3 hours, 3.3 mL of the monomeric Vinylimidazole (VI), N2After bubbling for half an hour, heating to 65 ℃, adding 0.042 g of initiator, reacting for 12 hours, taking out the membrane, soaking the membrane in DMF and ethanol, repeatedly washing the grafted membrane, and drying in vacuum to constant weight to obtain the polysulfone membrane (PSF-g-PVI) grafted with the polyvinyl imidazole, wherein the grafting degree of the polyvinyl imidazole is 0.21 mg/cm2。
Example 4:
0.1g of CMPSF and 60mL of a mixed solvent consisting of ethanol, water and DMF (volume ratio =1:1: 2) were put into a four-necked flask equipped with a stirrer, a condenser tube and a thermometer, and after swelling for 2 hours, 0.13g of 3-hydroxy-N, N-diethylaniline (HDEA) and 0.13g of triethylamine, N-diethylaniline (HDEA) were added2Protecting, stirring at the constant temperature of 75 ℃ for reaction for 8h, taking out the membrane, repeatedly washing by using a mixed solvent of ethanol and distilled water with the volume ratio of 1:1, and drying in vacuum to constant weight to obtain the modified polysulfone membrane PSF-DEA with the side chain bonded with the aromatic tertiary amine, wherein the bonding amount is 1.70 umol/cm2。
0.1g of PSF-DEA membrane was then added to 70mL of DMF and after swelling for 3 hours, 3.5 mL of the monomeric Vinylimidazole (VI), N2Bubbling for half an hour, heating to 70 deg.C, adding 0.045 g initiator, reacting for 12 h, taking out the membrane, soaking in DMF, ethanol, washing repeatedly, and collectingBranching the membrane, vacuum drying to constant weight to obtain polysulfone membrane (PSF-g-PVI) grafted with polyvinyl imidazole with grafting degree of 0.23 mg/cm2。
Polysulfone microporous filter membrane PSF-g-PVI grafted with polyvinyl imidazole and having adsorption and interception performance on toxic anions
An adsorption method: k with the concentration of 1-14mmol/L is prepared respectively2CrO4And Na3AsO4The pH of the aqueous solution was adjusted to 3 and 5, respectively, and 0.02 g of the microfiltration membrane PSF-g-PVI (example 1) was placed in 20mL of the aqueous solution, respectively, and then an adsorption experiment was performed at 25 ℃ in a water bath constant temperature shaker. PSF-g-PVI vs HCrO4 -The maximum adsorption amount of (2) is 11.8. mu. mol/cm2To H2AsO4 -The maximum adsorption capacity of the ions was 7.2. mu. mol/cm2And the ungrafted membrane CMPSF versus HCrO4 -And H2AsO4 -The ions are hardly adsorbed (see fig. 3).
And (3) a penetration method: at 4cm2The PSF-g-PVI membrane is a filter membrane, a self-made needle type filter (as shown in figure 2) is connected with a syringe; adding K with the initial concentration of 5mmol/L2CrO4And Na3AsO4The retention rate of two anions is almost 100% when the water solution passes through the filter membrane at a fixed flow rate in the range of 0-20mL, and the retention rate of two anions is kept above 95% when the permeation solution is increased to 60mL (as shown in figure 4), so that the PSF-g-PVI of the functional polysulfone filter membrane is used for treating HCrO4 -And H2AsO4 -The anion has strong retention capacity and can be used for sewage purification.
Claims (8)
1. The application of the polyvinyl imidazole functionalized polysulfone microfiltration membrane in adsorption and interception of toxic anions is characterized in that: the polyvinyl imidazole functionalized polysulfone microfiltration membrane consists of a polysulfone base membrane PSF and polyvinyl imidazole PVI, and has a structure shown in a formula (I):
。
2. the use of a polyvinylimidazole functionalized polysulfone microfiltration membrane according to claim 1 for the adsorption and rejection of toxic anions, wherein: the preparation method of the polyvinyl imidazole functionalized polysulfone microfiltration membrane comprises the following steps: taking a polysulfone membrane PSF as a base membrane, performing chloromethylation modification, and then bonding aromatic tertiary amine groups on the surface of the base membrane; and then placing the membrane in a dimethylformamide solution containing a vinyl imidazole monomer VI and an oil-soluble initiator, and carrying out graft polymerization on the membrane surface under the action of a redox type surface initiation system consisting of tertiary aromatic amine and BPO or AIBN to obtain the polyvinyl imidazole functionalized polysulfone microfiltration membrane PSF-g-PVI.
3. The use of a polyvinylimidazole functionalized polysulfone microfiltration membrane according to claim 2 for the adsorption and rejection of toxic anions, wherein: the preparation method comprises the following specific steps:
(1) preparing a modified polysulfone membrane PSF-DEA with a side chain bonded with aromatic tertiary amine: adding 0.1g of chloromethylated polysulfone membrane CMPSF into 60mL of mixed solvent of ethanol, water and N, N-dimethylformamide, swelling for 2h, adding 0.13g of reaction reagent 3-hydroxy-N, N-diethylaniline HDEA, and adding 0.12-0.13g of acid-binding agent and N2Stirring at the constant temperature of 70-80 ℃ under protection for reaction for 6-8h, taking out the membrane, repeatedly washing with a mixed solution of ethanol and distilled water in a volume ratio of 1:1, and drying in vacuum to constant weight to obtain a modified polysulfone membrane PSF-DEA with a side chain bonded with aromatic tertiary amine;
(2) preparing a polyvinyl imidazole functionalized polysulfone microfiltration membrane: 0.1g of PSF-DEA membrane was added to 70mL of DMF N, N-dimethylformamide, allowed to swell for 2 to 3 hours, and vinylimidazole VI, N was added2And after bubbling for half an hour, heating to 60-70 ℃, adding an initiator, reacting for 10-12 hours, taking out the membrane, respectively soaking the membrane in DMF (dimethyl formamide), repeatedly washing the grafted membrane with ethanol, and drying in vacuum to constant weight to obtain the polyvinyl imidazole functionalized polysulfone microfiltration membrane PSF-g-PVI.
4. A polyethylene according to claim 3The application of the imidazole functionalized polysulfone microfiltration membrane in adsorption and interception of toxic anions is characterized in that: in the mixed solvent of the ethanol, the water and the N, N-dimethylformamide in the step (1), the volume ratio of the ethanol to the water to the N, N-dimethylformamide is 1:1: 2; the acid-binding agent is Na2CO3、NaHCO3NaOH or triethylamine.
5. The use of a polyvinylimidazole functionalized polysulfone microfiltration membrane according to claim 3 for the adsorption and rejection of toxic anions, wherein: the dosage of the vinyl imidazole in the step (2) is 4.4-5% of the mass of the solution; the initiator is dibenzoyl peroxide (BPO) or Azobisisobutyronitrile (AIBN), and the dosage of the initiator is 1.4 percent of the mass of the vinyl imidazole.
6. Use according to claim 1, characterized in that: with CrO in an aqueous medium4 2-And AsO4 3-Two toxic anions are target removers, and the removal effect of the micro-filtration membrane PSF-g-PVI on the two target removers is measured by adopting an adsorption method and a permeation method.
7. Use according to claim 6, characterized in that: the adsorption method specifically comprises the following steps: k with the preparation concentration of 10mmol/L2CrO4Or Na3AsO4Adjusting pH of the aqueous solution to 3 and 5, respectively, accurately measuring area of 0.02 g of imidazole-functionalized microfiltration membrane PSF-g-PVI, cutting into pieces, placing into 20mL of the aqueous solution, respectively, performing adsorption experiment at 25 deg.C in a water bath constant temperature oscillator, and measuring HCrO in the supernatant by spectrophotometry (lambda =540 nm) and ICP-AES method, respectively4 -And H2AsO4 -Toxic anion concentration and calculate the respective adsorption capacity.
8. Use according to claim 6, characterized in that: the infiltration method comprises the following specific steps: k with the preparation concentration of 5mmol/L2CrO4Or Na3AsO4Dissolving in waterAdjusting the pH value to 3 and 5 respectively, sucking 80mL of 5mmol/L solution into an injector, preparing a needle filter by taking a PSF-g-PVI membrane as a filter membrane, and connecting the filter membrane with the injector; the solution is filtered by pushing the injector by hand, and the filter liquor is received by the container; the anion concentration in the filtrate was measured at different volume intervals and the respective removal rates were calculated.
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| CN108905656A (en) * | 2018-07-12 | 2018-11-30 | 中北大学 | A kind of grafting poly (sodium 4-styrenesulfonate) polysulfone millipore filtering membrane preparation method and application |
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| CN108905656A (en) * | 2018-07-12 | 2018-11-30 | 中北大学 | A kind of grafting poly (sodium 4-styrenesulfonate) polysulfone millipore filtering membrane preparation method and application |
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