CN102580582A - Aperture-adjustable pollution-resistant nanofiltration membrane and preparation method - Google Patents
Aperture-adjustable pollution-resistant nanofiltration membrane and preparation method Download PDFInfo
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Abstract
The invention discloses an aperture-adjustable pollution-resistant nanofiltration membrane and a preparation method. The preparation method comprises the following steps of: (1) adding nitrogen methyl pyrrolidone, polyvinylpyrrolidone and the mixture of azido polysulfone and polysulfone into a container, and stirring to obtain an azido polysulfone microporous membrane through an immerse precipitation transformation method; and (2) adding copper sulfate pentahydrate and alkynyl methoxypolyethylene glycol into a methanol aqueous solution, mixing uniformly to obtain a mixed solution, and adding the azido polysulfone microporous membrane into the mixed solution; introducing nitrogen; adding sodium ascorbate and introducing nitrogen; sealing the container, and heating for reaction; and taking out the membrane, rinsing, drying and weighing to obtain the aperture-adjustable pollution-resistant nanofiltration membrane. Through the invention, the aperture and aperture distribution of the microporous membrane can be adjusted, and the pollution resistance of the microporous membrane is improved.
Description
Technical field
The present invention relates to regulatable anti-pollution NF membrane in a kind of aperture and preparation method.
Background technology
NF membrane is a kind of pressure drive membrane of size of separation between counter-infiltration and ultrafiltration.Through the development of two more than ten years, NF membrane has obtained extensive use in water treatment technologies such as water softening, pure water preparation, middle water reuse and desalinizations.The development of life science, bioengineering, pharmaceuticals industry and food industry for NF membrane provides the application space of more attractive, is also had higher requirement to the NF membrane material: 1) anti-pollution simultaneously; 2) have accurate controlled pore size and single relatively pore-size distribution.Present NF membrane material can't satisfy above-mentioned requirements: at present NF membrane anti-fouling performance difference is main relevant with the hydrophily difference of membrane material, and the aperture structure poor controllability this be that essence by present phase inversion and interfacial polymerization determines.
Calendar year 2001 Sharpless etc. propose the notion of " click chemistry (Click chemistry) ", and its thought is to utilize minority to be close to perfectly reaction, through the synthetic diversified compound of effective, modular approach.Foremost click-reaction is 1 of copper catalysis organic azide and an alkynes, the 3-Dipolar Cycloaddition.The characteristics of click chemistry comprise: the empty G&W of the modularization reactant that obtains easily, harmless reaction dissolvent, high reaction yield, reaction pair is insensitive, to the compatibility of active group, have zone and stereoselectivity.Because above-mentioned advantage, click chemistry has become macromolecular solid has been fixed on one of effective method of the various surfaces of solids.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, provide a kind of aperture regulatable anti-pollution NF membrane.
Second purpose of the present invention provides a kind of mild condition, simple to operate, is applicable to the preparation method of the regulatable anti-pollution NF membrane in aperture of suitability for industrialized production.
Technical scheme of the present invention is summarized as follows:
The preparation method of the regulatable anti-pollution NF membrane in aperture comprises the steps:
(1) mixture with 77～81 mass parts n-formyl sarcolysine base pyrrolidones, 7～9 mass parts polyvinylpyrrolidones and nitrine polysulfones and polysulfones joins in the container; Stir 14～48h down at 30～65 ℃, utilize the immersion precipitation phase inversion to process nitrine polysulfones microporous barrier; The mixture of said nitrine polysulfones and polysulfones is to be mixed by 1.6～21 mass parts nitrine polysulfones, 0～18.9 mass parts polysulfones;
(2) in volumetric concentration is 0～70% methanol aqueous solution, add cupric sulfate pentahydrate and alkynyl polyethylene glycol monomethyl ether, mix, the acquisition mixed solution immerses said nitrine polysulfones microporous barrier in the said mixed solution; Logical nitrogen 10～30min; Add sodium ascorbate, continue logical nitrogen 10～30min; After seal of vessel, water-bath is heated to 30～60 ℃, reaction 0.5～5h; Film is taken out; Earlier with water rinse 2～5 times; Use methanol rinse again 2～5 times; Drying is weighed, and processes the regulatable anti-pollution NF membrane in aperture, and the mol ratio of azido group is 3～5: 0.1～2.0 on said cupric sulfate pentahydrate, alkynyl polyethylene glycol monomethyl ether, sodium ascorbate and the nitrine polysulfones microporous barrier: 3～25: 1.
Said polysulfones is that number-average molecular weight is the polysulfones of 18000-40000Dalton.
Said polyvinylpyrrolidone is the K30 or the K90 of technical grade.
The mean molecule quantity of poly glycol monomethyl ether is 120-5000 in the said alkynyl polyethylene glycol monomethyl ether.
The regulatable anti-pollution NF membrane in the aperture of method for preparing.
The present invention utilizes the click chemistry method that the polyethylene glycol (PEG) of the anti-protein adsorption of a series of different molecular weights is grafted to nitrine polysulfones microporous barrier surface; Regulate and control the aperture and the pore-size distribution of microporous barrier through the grafting of PEG; And improve the microporous barrier stain resistance, prepare the regulatable anti-pollution NF membrane in a series of apertures.
Advantage of the present invention is to utilize inversion of phases legal system film simple to operate; And the click chemistry prepared in reaction NF membrane gentle with reaction condition, that reaction efficiency is high; Chain property polymer through clicking the grafting different chain length can prepare the NF membrane in different apertures; Can change the character of film simultaneously according to the character of chain property polymer, obtain film of different nature.
Description of drawings
Among Fig. 1
A is a polysulfones 1H-NMR spectrogram;
B is a chloromethyl polysulphone 1H-NMR spectrogram;
C is a nitrine polysulfones 1H-NMR spectrogram.
Among Fig. 2
A is the 1H-NMR spectrogram of polysulfones;
B is the 1H-NMR spectrogram of alkynyl polyethylene glycol monomethyl ether 120;
C is the 1H-NMR spectrogram of alkynyl polyethylene glycol monomethyl ether 350;
D is the 1H-NMR spectrogram of alkynyl polyethylene glycol monomethyl ether 1300.
Among Fig. 3
A is the nitrine polysulfones microporous barrier infrared spectrum of embodiment 6 preparations;
B, c, d are respectively the infrared spectrum of the regulatable anti-pollution NF membrane in aperture of embodiment 7-9 preparation.
Fig. 4 is the nitrine polysulfones microporous barrier of embodiment 6 preparations and the graph of pore diameter distribution of the regulatable anti-pollution NF membrane in aperture that embodiment 7-9 prepares.A is the nitrine polysulfones microporous barrier graph of pore diameter distribution of embodiment 6 preparations; B, c, d are respectively the graph of pore diameter distribution of the regulatable anti-pollution NF membrane in aperture of embodiment 7-9 preparation.
Fig. 5 is polysulfones microporous barrier and the pure water of the regulatable anti-pollution NF membrane in aperture that embodiment 7,8 prepares and the flux detector of bovine serum albumin/phosphate buffer solution of embodiment 5 preparations.A is the change curve of polysulfones microporous barrier water flux in the test loop process of embodiment 5 preparations; B, c are respectively the change curve of the regulatable anti-pollution NF membrane in aperture water flux in the test loop process of embodiment 7,8 preparations.
Fig. 6 is polysulfones microporous barrier in test loop process the water flux relative recovery rate block diagram of the pure water recovery rate block diagram a of the polysulfones microporous barrier of embodiment 5 preparations and the regulatable anti-pollution NF membrane in aperture that embodiment 7,8 prepares for embodiment 5 preparations; B, c are respectively the relative recovery rate block diagram of the regulatable anti-pollution NF membrane in aperture water flux in the test loop process of embodiment 7,8 preparations.
Fig. 7 is the nitrine polysulfones microporous barrier and the water flux change curve of Tao Shi NF270 film in the profit system of embodiment 8 preparations.A is the normalized change curve of the adjustable anti-pollution NF membrane in aperture of embodiment 8 preparation test water flux and this film flux in pure water in the profit system; B is the normalized change curve of the NF270 of the Dow Chemical Company film at profit system test water flux and this film flux in pure water.
The specific embodiment
Below in conjunction with specific embodiment the present invention is further described.
The nitrine polysulfones is through behind the synthetic chloromethyl polysulphone of polysulfones chloromethylation step, carries out the Azide preparation again.The preparation of nitrine polysulfones is a known method, and conduct is not to qualification of the present invention for the present embodiment disclosed method, and implementation step is exemplified below:
50 gram polysulfones (number-average molecular weight is 26000), 500 grams of drying are anhydrous 1, and the 2-dichloroethanes joins in 1000 milliliters the there-necked flask; Add 1 gram anhydrous zinc chloride; Logical nitrogen 20min gets rid of the oxygen and the steam of system; Slowly Dropwise 50 restrains chloromethyl methyl ether; 40 ℃ of water-bath 4h are cooled to room temperature, in methyl alcohol deposition, filter, dry behind the purifying 2 times, obtain chloromethyl polysulphone.
30 gram chloromethyl polysulphones, 300 milliliters of dimethyl sulfoxide (DMSO)s are joined in 500 milliliters of round-bottomed flasks; Logical nitrogen 10min; Slowly add 19.5 gram Sodium azides; 70 ℃ of water-bath 48h; Be cooled to room temperature, with methanol extraction, filtration, 50 ℃ dry down.See that Fig. 1 (near a polysulfones 1H-NMR spectrogram δ=1.69ppm is-C
H 3Characteristic peak; B chloromethyl polysulphone 1H-NMR spectrogram occurs near δ=4.56ppm-C
H 2The Cl characteristic peak; C Azide polysulfones 1H-NMR spectrogram occurs near δ=4.23ppm-C
H 2N
3The group characteristic peak, δ=4.56ppm characteristic peak obviously reduces simultaneously).
Alkynyl polyethylene glycol monomethyl ether is by poly glycol monomethyl ether and 3-propargyl bromide prepared in reaction under alkali condition, and the practical implementation step is following:
(1) (0.01mol), 100ml THF joins in the 250ml round-bottomed flask for 1.2g, number-average molecular weight 120 with poly glycol monomethyl ether;
(2) slowly add NaH (0.6g, 30mmol);
(3) stir 4h down at 40 ℃;
(4) (1.5g 13mmol), reacts under 30 ℃ and spends the night to add the 3-propargyl bromide;
(5) reaction finishes the back with the HCl neutralization, revolves to steam to remove and desolvates, with extracted with diethyl ether three times.See near 1H-NMR spectrogram (appearance-C δ=2.50 of Fig. 2 b alkynyl polyethylene glycol monomethyl ether 120
HThe peak, near appearance-C δ=4.22ppm
H 2-characteristic peak is the reaction back and introduces the group characteristic peak).
Alkynyl polyethylene glycol monomethyl ether is by poly glycol monomethyl ether and 3-propargyl bromide prepared in reaction under alkali condition, and the practical implementation step is following:
(1) (0.01mo1), 100ml THF joins in the 250ml round-bottomed flask for 3.5g, number-average molecular weight 350 with poly glycol monomethyl ether;
(2) slowly add NaH (0.6g, 30mmol);
(3) stir 4h down at 40 ℃;
(4) (1.5g 13mmol), reacts under 30 ℃ and spends the night to add the 3-propargyl bromide;
(5) reaction finishes the back with the HCl neutralization, revolves to steam to remove and desolvates, with extracted with diethyl ether three times.See that Fig. 2 c is near 1H-NMR spectrogram (appearance-C δ=2.50 of alkynyl polyethylene glycol monomethyl ether 350
HThe peak, near appearance-C δ=4.22ppm
H 2-characteristic peak is the reaction back and introduces the group characteristic peak).
Embodiment 4
Alkynyl polyethylene glycol monomethyl ether is by poly glycol monomethyl ether and 3-propargyl bromide prepared in reaction under alkali condition, and the practical implementation step is following:
(1) (0.01mol), 100ml THF joins in the 250ml round-bottomed flask for 13g, number-average molecular weight 1300 with poly glycol monomethyl ether;
(2) slowly add NaH (0.6g, 30mmol);
(3) stir 4h down at 40 ℃;
(4) (1.5g 13mmol), reacts under 30 ℃ and spends the night to add the 3-propargyl bromide;
(5) reaction finishes the back with the HCl neutralization, thickening filtration, and the THF washing is used ether sedimentation, filtration drying.See that Fig. 2 d is near 1H-NMR spectrogram (appearance-C δ=2.50 of alkynyl polyethylene glycol monomethyl ether 1300
HThe peak, near appearance-C δ=4.22ppm
H 2-characteristic peak is the reaction back and introduces the group characteristic peak).
Embodiment 5 (being used for contrasting) with the adjustable anti-pollution NF membrane in aperture
The polysulfones microporous barrier is not add the nitrine polysulfones, only adds polysulfones, with immersion precipitation phase inversion preparation, the practical implementation step is following:
(1) 80 gram n-formyl sarcolysine base pyrrolidones, 7 gram polyvinylpyrrolidones (K30 of technical grade) and 13 gram polysulfones (number-average molecular weight is 26000) join in 250 milliliters of round-bottomed flasks;
(2) 60 ℃ of mechanical agitation 24h;
(3) 50 ℃ of discontinuous degassing 12h;
(4) be cooled to room temperature, knifing on the glass plate of cleaning, and put into the pure water coagulating bath immediately;
(5) film is soaked preservation in the pure water of cleaning.
The anti-fouling performance test result of embodiment 5 is seen Fig. 5 a, Fig. 6 a.
Embodiment 6
Nitrine polysulfones microporous barrier is by polysulfones and nitrine polysulfones according to a certain percentage, with the preparation of immersion precipitation phase inversion, the practical implementation step is following:
The mixture of (1) 80 gram n-formyl sarcolysine base pyrrolidones, 7 gram polyvinylpyrrolidones (K30 of technical grade) and polysulfones (number-average molecular weight is 26000) and nitrine polysulfones joins in 250 milliliters of round-bottomed flasks; The mixture of polysulfones and nitrine polysulfones is to be mixed by 7.8 gram polysulfones (number-average molecular weight is 26000) and 5.2 gram nitrine polysulfones;
(2) 60 ℃ of mechanical agitation 24h;
(3) 50 ℃ of discontinuous degassing 12h;
(4) be cooled to room temperature, knifing on the glass plate of cleaning, and put into the pure water coagulating bath immediately;
(5) film is soaked preservation in the pure water of cleaning.Nitrine polysulfones microporous barrier infrared spectrum sees that Fig. 3 a is (at 2101cm
-1Near appearance-N
3The group characteristic peak).
Embodiment 7
The regulatable anti-pollution NF membrane in aperture on the film of embodiment 6 preparation, prepares with the alkynyl polyethylene glycol monomethyl ether of click chemistry reactive grafting different molecular weight, and the practical implementation step is following:
(1) the nitrine polysulfones microporous barrier with embodiment 6 preparations is cut into 25cm
2, be immersed in volumetric concentration after drying is weighed and be in 50% the methanol aqueous solution;
(2) in reaction tube, adding 30 ml volumes concentration is 50% methanol aqueous solution; Add cupric sulfate pentahydrate and alkynyl polyethylene glycol monomethyl ether (Mn 120) (embodiment 2 preparations), mix;
(3) nitrine polysulfones microporous barrier is taken out from methanol aqueous solution, water is rinsed the mixed liquor of putting into above-mentioned reaction tube well; Logical nitrogen 10min; Add sodium ascorbate, and continue logical nitrogen 10min; After the reaction tube sealing, water-bath is heated to 50 ℃ of clock reaction 5h; Film is taken out; Earlier with water rinse 3 times, use methanol rinse again 3 times, drying is weighed; Process the regulatable anti-pollution NF membrane in aperture, the mol ratio of azido group is 4: 2: 10 on said cupric sulfate pentahydrate, alkynyl polyethylene glycol monomethyl ether, sodium ascorbate and the nitrine polysulfones microporous barrier: 1.The infrared spectrum of the regulatable anti-pollution NF membrane in aperture sees that Fig. 3 b is (at 2101cm
-1Near-N
3The complete obiteration of group characteristic peak).
Embodiment 8
The regulatable anti-pollution NF membrane in aperture on the film of embodiment 6 preparation, prepares with the alkynyl polyethylene glycol monomethyl ether of click chemistry reactive grafting different molecular weight, and the practical implementation step is following:
(1) with embodiment 7 step (1);
(2) in reaction tube, adding 30 ml volumes concentration is 50% methanol aqueous solution; Add cupric sulfate pentahydrate and alkynyl polyethylene glycol monomethyl ether (Mn 350) (embodiment 3 preparations), mix;
(3) with embodiment 7 steps (3); The infrared spectrum of the regulatable anti-pollution NF membrane in aperture sees that Fig. 3 c is (at 2101cm
-1Near-N
3The complete obiteration of group characteristic peak).
Embodiment 9
The regulatable anti-pollution NF membrane in aperture on the film of embodiment 6 preparation, prepares with the alkynyl polyethylene glycol monomethyl ether of click chemistry reactive grafting different molecular weight, and the practical implementation step is following:
(1) with embodiment 7 step (1);
(2) in reaction tube, adding 30 ml volumes concentration is 50% methanol aqueous solution; Add cupric sulfate pentahydrate and alkynyl polyethylene glycol monomethyl ether (Mn 1300) (embodiment 4 preparations), mix;
(3) with embodiment 7 steps (3); The infrared spectrum of the regulatable anti-pollution NF membrane in aperture sees that Fig. 3 d is (at 2101cm
-1Near-N
3The group characteristic group obviously reduces).
Embodiment 10
The pore-size distribution of three kinds of regulatable anti-pollution NF membrane in aperture of the nitrine polysulfones microporous barrier of embodiment 6 preparations and embodiment 7-9 preparation characterizes, and the practical implementation step is following:
(1) disposes the polyglycol solution of 10ppm respectively; Select a series of molecular weight polyethylene glycol for use, be respectively molecular weight 400, molecular weight 600, molecular weight 1000, molecular weight 2000, molecular weight 6000, molecular weight 10000, molecular weight 20000, molecular weight 100000.
(2) film is put into testing arrangement, former film is under 0.1MPa, and NF membrane inserts the pure water precompressed and stablizes 1h under 0.6MPa, change pure water into polyglycol solution then, test.Test the absorbance of stoste respectively and see through the absorbance of liquid, make indicator with iodine and liquor kalii iodide, the calculating membrane is to the rejection of this polyethylene glycol.
The rejection of a series of polyethylene glycol that (3) will test converges into pore size distribution curve and sees Fig. 4 (average pore size is in the 2.01nm scope for the nitrine PS membrane pore size distribution curve of a embodiment 6 preparation, pore-size distribution broad; B, c, d are respectively the pore size distribution curve of the adjustable anti-pollution NF membrane in aperture of embodiment 7-9 preparation, and pore-size distribution narrows down gradually, and average pore size is reduced to 0.8-1.5nm respectively, 0.7-0.92nm and 0.5-0.75nm).
The aperture regulatable anti-pollution NF membrane antipollution test of embodiment 7-9 preparation characterizes, and the practical implementation step is following:
(1) preparation 1000ppm bovine serum albumin/phosphate buffer solution.Difference weighing 1g bovine serum albumin, 8.0g sodium chloride.0.2g potassium chloride, the 1.44g sodium hydrogen phosphate, the 0.24g potassium dihydrogen phosphate is settled in the volumetric flask of 1L, and behind the ultrasonic 5min, low temperature is preserved.
(2) the regulatable anti-pollution NF membrane in aperture (the regulatable anti-pollution NF membrane in aperture of embodiment 7-9 preparation is tested respectively) is put into test suite, at first insert pure water, precompressed under 0.4MPa, the flux of every 5min recording film is until stable.
(3) after the flux stabilized of film, change pure water into bovine serum albumin/phosphate buffer solution, every 5min record flux no longer changes until the flux of film, and this moment, flux was designated as J
o
(4) claim that 4g NaOH is settled to 1L, the sodium hydroxide solution of preparation 0.1mol/L.
(5) bovine serum albumin/phosphate buffer solution is changed into sodium hydroxide solution in (4), film is washed 30min, change pure water washing 3 times then into, each 5min.
(6) insert pure water, test membrane is to the flux J of pure water
v
(7) according to the above-mentioned steps loop test more than three times.
(8) the water flux recovery rate of film is designated as R
FR, according to formula R
FR=J
v/ J
oCalculate.See that (a is the result of the polysulfones microporous barrier of embodiment 5 preparation to Fig. 5, is reducing obviously through water flux behind three loop tests; B, c are respectively the adjustable anti-pollution NF membrane in aperture of embodiment 7,8 preparations; Basically remaining unchanged through water flux behind three loop tests); (a reduces through the relative recovery rate of water flux in the loop test process for the polysulfones microporous barrier of embodiment 5 preparations Fig. 6 gradually; Behind three loop tests, approximately be reduced to original 40%-50%; B, c are respectively the adjustable anti-pollution NF membrane in aperture of embodiment 7,8 preparations in the loop test process, and the relative recovery rate of water flux remains unchanged basically, and flux is lower than 5%)
Embodiment 12
The regulatable anti-pollution NF membrane in aperture, process with following method:
(1) mixture with 77 mass parts n-formyl sarcolysine base pyrrolidones, 9 mass parts polyvinylpyrrolidones (technical grade K90) and nitrine polysulfones and polysulfones (number-average molecular weight is 40000Dalton) joins in the container; Stir 48h down at 30 ℃, utilize the immersion precipitation phase inversion to process nitrine polysulfones microporous barrier; The mixture of nitrine polysulfones and polysulfones is to be mixed by 1.6 mass parts nitrine polysulfones, 18.9 mass parts polysulfones;
(2) in water, add cupric sulfate pentahydrate and alkynyl polyethylene glycol monomethyl ether (mean molecule quantity of poly glycol monomethyl ether is 5000 in the alkynyl polyethylene glycol monomethyl ether), mix, obtain mixed solution, nitrine polysulfones microporous barrier is immersed in the mixed solution; Logical nitrogen 10min; Add sodium ascorbate, continue logical nitrogen 10min; After seal of vessel, water-bath is heated to 30 ℃, reaction 5h; Film is taken out, with water rinse 2 times, use methanol rinse again 2 times earlier, drying is weighed, and processes the regulatable anti-pollution NF membrane in aperture; The mol ratio of azido group is 3: 2.0: 10 on cupric sulfate pentahydrate, alkynyl polyethylene glycol monomethyl ether, sodium ascorbate and the nitrine polysulfones microporous barrier: 1.
Embodiment 13
The regulatable anti-pollution NF membrane in aperture, process with following method:
(1) mixture with 80 mass parts n-formyl sarcolysine base pyrrolidones, 7 mass parts polyvinylpyrrolidones (technical grade K90) and nitrine polysulfones and polysulfones (number-average molecular weight is 18000Dalton) joins in the container; Stir 36h down at 50 ℃, utilize the immersion precipitation phase inversion to process nitrine polysulfones microporous barrier; The mixture of nitrine polysulfones and polysulfones is to be mixed by 10 mass parts nitrine polysulfones, 10 mass parts polysulfones;
(2) in volumetric concentration is 60% methanol aqueous solution; Add cupric sulfate pentahydrate and alkynyl polyethylene glycol monomethyl ether (mean molecule quantity of poly glycol monomethyl ether is 4000 in the alkynyl polyethylene glycol monomethyl ether); Mix; Obtain mixed solution, nitrine polysulfones microporous barrier is immersed in the mixed solution; Logical nitrogen 20min; Add sodium ascorbate, continue logical nitrogen 20min; After seal of vessel, water-bath is heated to 45 ℃, reaction 3h; Film is taken out, with water rinse 4 times, use methanol rinse again 3 times earlier, drying is weighed, and processes the regulatable anti-pollution NF membrane in aperture; The mol ratio of azido group is 4: 0.1: 25 on cupric sulfate pentahydrate, alkynyl polyethylene glycol monomethyl ether, sodium ascorbate and the nitrine polysulfones microporous barrier: 1.
Embodiment 14
The regulatable anti-pollution NF membrane in aperture, process with following method:
(1) 81 mass parts n-formyl sarcolysine base pyrrolidones, 8 mass parts polyvinylpyrrolidones (technical grade K30) and 21 mass parts nitrine polysulfones are joined in the container; Stir 14h down at 65 ℃, utilize the immersion precipitation phase inversion to process nitrine polysulfones microporous barrier;
(2) in volumetric concentration is 70% methanol aqueous solution; Add cupric sulfate pentahydrate and alkynyl polyethylene glycol monomethyl ether (mean molecule quantity of poly glycol monomethyl ether is 2000 in the alkynyl polyethylene glycol monomethyl ether); Mix; Obtain mixed solution, nitrine polysulfones microporous barrier is immersed in the mixed solution; Logical nitrogen 30min; Add sodium ascorbate, continue logical nitrogen 30min; After seal of vessel, water-bath is heated to 60 ℃, reaction 0.5h; Film is taken out; Earlier with water rinse 5 times, use methanol rinse again 5 times, drying is weighed; Process the regulatable anti-pollution NF membrane in aperture, the mol ratio of azido group is 5: 1.0: 3 on said cupric sulfate pentahydrate, alkynyl polyethylene glycol monomethyl ether, sodium ascorbate and the nitrine polysulfones microporous barrier: 1.
Through testing proof: the aperture regulatable anti-pollution NF membrane pore-size distribution of embodiment 12-14 preparation characterizes and the antipollution test, and the result shows that its membrane aperture test of the adjustable anti-pollution NF membrane in aperture, the film that prepare with embodiment 7-9 pollute test result and Changing Pattern is similar.
Claims (5)
1. the preparation method of the regulatable anti-pollution NF membrane in aperture is characterized in that comprising the steps:
(1) mixture with 77～81 mass parts n-formyl sarcolysine base pyrrolidones, 7～9 mass parts polyvinylpyrrolidones and nitrine polysulfones and polysulfones joins in the container; Stir 14～48h down at 30～65 ℃, utilize the immersion precipitation phase inversion to process nitrine polysulfones microporous barrier; The mixture of said nitrine polysulfones and polysulfones is to be mixed by 1.6～21 mass parts nitrine polysulfones, 0～18.9 mass parts polysulfones;
(2) in volumetric concentration is 0～70% methanol aqueous solution, add cupric sulfate pentahydrate and alkynyl polyethylene glycol monomethyl ether, mix, the acquisition mixed solution immerses said nitrine polysulfones microporous barrier in the said mixed solution; Logical nitrogen 10～30min; Add sodium ascorbate, continue logical nitrogen 10～30min; After seal of vessel, water-bath is heated to 30～60 ℃, reaction 0.5～5h; Film is taken out; Earlier with water rinse 2～5 times; Use methanol rinse again 2～5 times; Drying is weighed, and processes the regulatable anti-pollution NF membrane in aperture, and the mol ratio of azido group is 3～5: 0.1～2.0 on said cupric sulfate pentahydrate, alkynyl polyethylene glycol monomethyl ether, sodium ascorbate and the nitrine polysulfones microporous barrier: 3～25: 1.
2. the regulatable anti-pollution NF membrane in aperture according to claim 1 is characterized in that said polysulfones is that number-average molecular weight is the polysulfones of 18000-40000Dalton.
3. the regulatable anti-pollution NF membrane in aperture according to claim 1 is characterized in that said polyvinylpyrrolidone is the K30 or the K90 of technical grade.
4. the regulatable anti-pollution NF membrane in aperture according to claim 1 is characterized in that the mean molecule quantity of poly glycol monomethyl ether in the said alkynyl polyethylene glycol monomethyl ether is 120-5000.
5. the regulatable anti-pollution NF membrane in aperture of the method for one of claim 1-4 preparation.
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| CN103736408A (en) * | 2013-12-31 | 2014-04-23 | 中科院广州化学有限公司 | Polysulfone porous film in response to temperature and acidity, preparation method and application of polysuffone porous film |
| CN103736408B (en) * | 2013-12-31 | 2015-11-18 | 中科院广州化学有限公司 | A kind of polysulfone porous membrane to temperature, acidity response and preparation method thereof and application |
| CN104971633A (en) * | 2015-06-18 | 2015-10-14 | 安徽师范大学 | Preparation method of composite forward osmosis membrane made from polyaramid |
| CN105344257A (en) * | 2015-11-19 | 2016-02-24 | 中国科学院山西煤炭化学研究所 | 1,2,3,4-tetrazole-containing polyacrylonitrile ultrafiltration membrane and preparation method thereof |
| CN105344257B (en) * | 2015-11-19 | 2017-12-19 | 中国科学院山西煤炭化学研究所 | Polyacrylonitrile ultrafiltration film and preparation method containing 1,2,3,4 tetrazole |
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Application publication date: 20120718 |