CN105536575A - Solvent-resistant nanofiltration mixed matrix membrane, and making method and application thereof - Google Patents
Solvent-resistant nanofiltration mixed matrix membrane, and making method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of organic solvent nanofiltration, and especially relates to a solvent-resistant nanofiltration mixed matrix membrane with excellent solvent resistance in solvents with different polarities, and a making method and an application thereof. The making method of the membrane comprises the following steps: sequentially coating the surface of a water fully-absorbed polyacrylonitrile ultrafilter membrane with a solution A and a solution B, and drying the solution A and the solution B to obtain the solvent-resistant nanofiltration mixed matrix membrane, wherein the solution A is an polydopamine nanoparticle dispersed aqueous polyethyleneimine solution, and the solution B is an organic trimesoyl chloride solution. The method has the advantages of abundant raw materials for producing the membrane, low price, simple membrane production process, and mild conditions. The solvent-resistant nanofiltration mixed matrix membrane made in the invention has suitable separation performance, has higher solvent resistance than pure polymer membranes, and can be applied in the solvents with different polarities.
Description
Technical field
The invention belongs to organic solvent nanofiltration technical field, particularly a kind of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve having outstanding solvent resistance in the solvent of opposed polarity and its preparation method and application.
Background technology
Organic solvent nanofiltration be a kind of emerging take selective membrane as medium, ORGANIC SOLVENT MIXTURES is carried out to the technology of abstraction and purification, because it is easy and simple to handle, green high-efficient and be subject to extensive concern, it is unusual to recycle at catalyst recovery, solvent, refine oil and play a part in the chemical process such as pharmaceutical industry.The core component of organic solvent nanofiltration system is organic solvent nanofiltration film, and desirable organic solvent nanofiltration film should possess good solvent resistance and separating property simultaneously.At present, polymeric membrane has good processing characteristics and lower cost due to it, is considered to the most promising material in organic solvent nanofiltration field.But because macromolecular chain is comparatively fine and close in low swelling lower arrangement, make anti-swelling character and permeation flux often present shifting trend, the polymeric membrane namely with good swelling resistance often has comparatively small throughput, and vice versa.Therefore, exploitation has the significant challenge that good swelling resistance and high-throughout membrane material are still solvent resistant NF membrane field concurrently.
For this target, researcher has carried out a large amount of work, as embedded Nano filling in polymeric membrane.Due to Nano filling self, there is permeable duct on the one hand or form regulatable passage with high molecular interface; Nano filling can disturb polymer segment to arrange on the other hand, the spacing between regulation and control segment.The advantage of these two aspects is not only solvent molecule and spreads in film and provide favourable passage, improves the permeation flux of film, and effectively enhances the solvent resistance of film.Such as, but traditional Nano filling mostly is inorganic filler, silica, zeolite etc., compatible poor between itself and macromolecular chain, easily form defect in interface, greatly reduce the separating property of film.Although many researchers adopt multiple strategy to go to eliminate mixed substrate membrane containing nano-grade molecular sieve boundary defect, between continuous phase and decentralized photo, still lack strong interaction, still cannot ensure that film has good anti-swelling.Therefore, preparation has excellent solvent resistance and suitable separating property solvent resistant NF membrane still needs to be explored.
Summary of the invention
The object of this invention is to provide a kind of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve and its preparation method and application, described film possesses outstanding solvent resistance and suitable separating property.
The technical solution used in the present invention is as follows:
A kind of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve, is obtained by laxative remedy: polyacrylonitrile (PAN) ultrafiltration membrane surface after fully absorbing water applies solution A and B solution successively, namely obtains described solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve after drying; Described solution A be poly-dopamine nanoparticulate dispersed in the aqueous phase solution of polymine, described B solution is the organic solution of pyromellitic trimethylsilyl chloride.
The preferred molecular cut off of described polyacrylonitrile ultrafiltration film is at 50-100kDa.
In described solution A, the mass ratio of polymine and poly-dopamine nano particle is 100:0.1-0.5; Polymine and Na
2cO
3mass ratio be 40:0.8-1.2; The mass ratio of polymine and deionized water is 1:23-25.
Wherein, during preparation solution A, first polymine is fully dissolved in deionized water, under the condition stirred, add Na subsequently
2cO
3with poly-dopamine powder of nanometric particles, at room temperature ultrasonic process 0.5-1h.Also can dissolve in deionized water with the aq. polyethyleneimine that concentration is 50wt%.
Described solution B is the solution that pyromellitic trimethylsilyl chloride is dissolved in n-hexane or normal heptane, and the mass concentration of pyromellitic trimethylsilyl chloride is 1-2%.
When coating A and B solution, respectively corresponding solution is coated in polyacrylonitrile ultrafiltration film surface 5-10min, then except the solution of striping excess surface.Concrete, the placed angle of adjustable film, makes the solution of film excess surface naturally flow down.
Described drying is prior to 1-2h dry under room temperature condition, then in 60 DEG C of dry 2-3h.
Concrete, preparation method's step is as follows:
(1) preparation has the polymine aqueous phase solution of poly-dopamine nanoparticulate dispersed.First taking a certain amount of mass fraction is that 50% aq. polyethyleneimine dissolves in deionized water, fully stirs 30min, add Na subsequently under the condition stirred under room temperature
2cO
3with poly-dopamine powder of nanometric particles, at room temperature ultrasonic process 1h is to reach the homodisperse effect of nanoscale.In aqueous phase solution, the mass ratio of polymine and poly-dopamine nano particle is 100:0.1-0.5; Polymine and Na
2cO
3mass ratio be 40:1; The mass ratio of polymine and deionized water is 1:24;
(2) pyromellitic trimethylsilyl chloride organic phase solution is prepared.The pyromellitic trimethylsilyl chloride taking certain mass is dissolved in n-hexane or normal heptane solvent, fully stirs 1h under room temperature.In organic phase solution, the mass ratio of pyromellitic trimethylsilyl chloride and n-hexane or normal heptane is 1:49;
(3) first by molecule rejection be the polyacrylonitrile ultrafiltration film surface submergence of 100kDa in deionized water after 30min, pour out deionized water; Then the aqueous phase solution of preparation in (1) is coated in PAN film surface 10min, removes unnecessary aqueous phase solution; Finally organic phase solution in (2) is coated in film surface 10min, removes unnecessary organic phase solution;
(4) dry 1h under film prepared in (3) being placed in room temperature condition, then places it in the constant temperature blast drying oven 2h of 60 DEG C, obtains poly-dopamine nano particle and embeds solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve in thin polyamide active layer.
In described film, poly-dopamine nano particle is 0.1-0.5% relative to the mass percent of polymine (PEI).Gained film can called after MMM-PDNPs-
x, wherein X=0.1,0.2,0.3,0.5.
Described film is used for organic solvent nanofiltration, be preferred for the opposed polarity organic solvent nanofiltration such as normal heptane, toluene, isopropyl alcohol and ethyl acetate, be specially adapted to isopropyl alcohol nanofiltration, the prepared area of mixed substrate membrane containing nano-grade molecular sieve in isopropyl alcohol is swelling is all less than 1.9%, adsorb and be swellingly all less than 27%, be 10bar at both sides differential pressure of membrane, when operating temperature is room temperature, isopropyl alcohol permeation flux is 12.3-23.1L/m
2h.
The invention belongs to organic solvent nanofiltration technical field, particularly a kind of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve having outstanding solvent resistance in the solvent of opposed polarity and its preparation method and application.Described solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve is the solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve embedded by poly-dopamine nano particle in thin polyamide active layer.Described matrix membrane shows suitable separating property, has excellent solvent resistance in different polar solvents.
This research is subject to bioadhesive effect and inspires in mechanism, dopamine can in atmosphere by its oligomer generation spontaneous oxidation, covalency polymerization and non-covalent self assembly form poly-dopamine nano particle (PDNPs), owing to tightly can adhere to each other with the form of covalent bond and hydrogen bond between PDNPs and PEI segment, thus the motion of polymer segment can be suppressed, therefore, PDNPs is embedded in polyamide active layer, not only can effectively suppress PEI sub-chain motion, improve the swelling resistance of mixed substrate membrane containing nano-grade molecular sieve, and the non-selective hole of PEI and PDNPs interface can be eliminated.In addition, similar to inorganic nano-filler, PDNPs can effectively disturb segment to arrange, regulation and control chain certain distance, the separating property of reinforced film.
Compared with prior art, tool has the following advantages in the present invention:
The present invention prepares the abundant raw material of membrane material, cheap, and film preparation process is simple, mild condition.Prepared solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve shows suitable separating property, has outstanding solvent resistance, can be applied in the solvent of opposed polarity than pure polymeric membrane.
Accompanying drawing explanation
Fig. 1 is the transmission electron microscope photo of poly-dopamine nano particle (PDNPs);
Fig. 2 is the stereoscan photograph on MMM-PDNPs-0.5 film surface;
Fig. 3 is the stereoscan photograph of MMM-PDNPs-0.5 film section;
Fig. 4 is PAN supporting layer, PAN/PEI film and MMM-PDNPs-
xfilm surface contact angle figure;
Fig. 5 is PAN supporting layer, PAN/PEI film and MMM-PDNPs-
xsolvent in area swelling figure, the figure of film at room temperature in normal heptane, toluene, isopropyl alcohol and ethyl acetate four kinds of solvents is followed successively by normal heptane, isopropyl alcohol, toluene and ethyl acetate;
Fig. 6 is PAN supporting layer, PAN/PEI film and MMM-PDNPs-
xsolvent in absorption swelling figure, the figure of film at room temperature in normal heptane, toluene, isopropyl alcohol and ethyl acetate four kinds of solvents is followed successively by normal heptane, isopropyl alcohol, toluene and ethyl acetate;
Fig. 7 is at room temperature, both sides differential pressure of membrane be 4 and 10bar time PDNPs content to normal heptane permeation flux effect diagram;
Fig. 8 is at room temperature, both sides differential pressure of membrane be 4 and 10bar time PDNPs content to toluene permeation flux effect diagram;
Fig. 9 is at room temperature, both sides differential pressure of membrane be 4 and 10bar time PDNPs content to isopropyl alcohol permeation flux effect diagram;
Figure 10 is at room temperature, both sides differential pressure of membrane be 4 and 10bar time PDNPs content to ethyl acetate permeation flux effect diagram;
Figure 11 is PAN/PEI and MMM-PDNPs-
xat room temperature, both sides differential pressure of membrane is 10bar to film, the cutoff performance curve of different molecular weight polyethylene glycol when solvent is isopropyl alcohol; Described curve is corresponding in turn to MMM-PDNPs-0.5 from top to bottom
,mMM-PDNPs-0.3, MMM-PDNPs-0.2, MMM-PDNPs-0.1 and PAN/PEI;
Figure 12 be MMM-PDNPs-0.1 film at room temperature, both sides differential pressure of membrane is 10bar, solute to be molecular weight be 1000 polyethylene glycol, long period of operation stability diagram when solvent is isopropyl alcohol.
Detailed description of the invention
With specific embodiment, technical scheme of the present invention is described below, but protection scope of the present invention is not limited thereto:
In following examples, the aqueous solution of poly-dopamine nano particle is with reference to K.Y.Ju, Y.Lee, S.Lee, S.B.
Implement ParkandJ.K.Lee,
biomacromolecules, 2011,12,625 are prepared.Example 1
The aqueous solution of the poly-dopamine nano particle of first preparation, carrys out collecting by filtration and gather dopamine nano particle, and priority deionized water and ethanol cleans 2 times respectively with the PAN milipore filter that molecular cut off is 100kDa.Finally poly-dopamine nano particle drying in the vacuum drying oven of 60 DEG C of collecting is obtained poly-dopamine powder of nanometric particles.
The polymine taking 4g50wt% is dissolved in 46g deionized water, fully stirs under room temperature, adds the Na of 0.05g subsequently
2cO
3gather dopamine powder of nanometric particles with 0.002g, at room temperature ultrasonic process 1h obtains solution A;
Taking 1g pyromellitic trimethylsilyl chloride is dissolved in 49g n-hexane, fully stirs 1h and obtain B solution under room temperature;
First be that the polyacrylonitrile ultrafiltration film surface submergence of 100kDa pours out deionized water after 30min in deionized water by molecule rejection.Subsequently solution A is coated in PAN film surface 10min, removes unnecessary aqueous phase solution.Finally B organic phase solution is coated in film surface 10min, and removes unnecessary organic phase solution.
Dry 1h under film being placed in room temperature condition, is then placed on the constant temperature blast drying oven 2h of 60 DEG C by film.Gained film is named as MMM/PDNPs-0.1, and PDNPs filler is 0.1% relative to the mass percent of PEI.
Fig. 4 shows the contact angle on MMM/PDNPs-0.1 film surface; It is swelling and adsorb swelling that Fig. 5 and 6 respectively illustrates the area of MMM/PDNPs-0.1 film at room temperature in normal heptane, toluene, isopropyl alcohol and ethyl acetate four kinds of solvents; Fig. 7,8,9 and 10 respectively illustrates MMM/PDNPs-0.1 film at room temperature, both sides differential pressure of membrane be 4 and 10bar time normal heptane, toluene, isopropyl alcohol and ethyl acetate permeation flux; Figure 11 shows MMM/PDNPs-0.1 film at room temperature, and both sides differential pressure of membrane is 10bar, the cutoff performance curve of different molecular weight polyethylene glycol when solvent is isopropyl alcohol; Figure 12 shows MMM/PDNPs-0.1 film at room temperature, and both sides differential pressure of membrane is 10bar, solute to be molecular weight be 1000 polyethylene glycol, long period of operation stability when solvent is isopropyl alcohol.
Embodiment 2
The method of embodiment 1 is adopted to prepare poly-dopamine powder of nanometric particles.
The polymine taking 4g50wt% is dissolved in 46g deionized water, fully stirs under room temperature, adds the Na of 0.05g subsequently
2cO
3gather dopamine powder of nanometric particles with 0.004g, at room temperature ultrasonic process 1h obtains solution A;
Taking 1g pyromellitic trimethylsilyl chloride is dissolved in 49g n-hexane, fully stirs 1h and obtain B solution under room temperature;
First be that the polyacrylonitrile ultrafiltration film surface submergence of 100kDa pours out deionized water after 30min in deionized water by molecule rejection.Subsequently solution A is coated in PAN film surface 10min, removes unnecessary aqueous phase solution.Finally B organic phase solution is coated in film surface 10min, and removes unnecessary organic phase solution.
Dry 1h under film being placed in room temperature condition, is then placed on the constant temperature blast drying oven 2h of 60 DEG C by film.Gained film is named as MMM/PDNPs-0.2, represents that PDNPs filler is 0.2% relative to the mass percent of PEI.
Fig. 4 shows the contact angle on MMM/PDNPs-0.2 film surface; It is swelling and adsorb swelling that Fig. 5 and 6 respectively illustrates the area of MMM/PDNPs-0.2 film at room temperature in normal heptane, toluene, isopropyl alcohol and ethyl acetate four kinds of solvents; Fig. 7,8,9 and 10 respectively illustrates MMM/PDNPs-0.2 film at room temperature, both sides differential pressure of membrane be 4 and 10bar time normal heptane, toluene, isopropyl alcohol and ethyl acetate permeation flux; Figure 11 shows MMM/PDNPs-0.2 film at room temperature, and both sides differential pressure of membrane is 10bar, the cutoff performance curve of different molecular weight polyethylene glycol when solvent is isopropyl alcohol.
Embodiment 3
The method of embodiment 1 is adopted to prepare poly-dopamine powder of nanometric particles.
The polymine taking 4g50wt% is dissolved in 46g deionized water, fully stirs under room temperature, adds the Na of 0.05g subsequently
2cO
3gather dopamine powder of nanometric particles with 0.006g, at room temperature ultrasonic process 1h obtains solution A;
Taking 1g pyromellitic trimethylsilyl chloride is dissolved in 49g n-hexane, fully stirs 1h and obtain solution B under room temperature;
First be that the polyacrylonitrile ultrafiltration film surface submergence of 100kDa pours out deionized water after 30min in deionized water by molecule rejection.Subsequently solution A is coated in PAN film surface 10min, removes unnecessary aqueous phase solution.Finally B organic phase solution is coated in film surface 10min, and removes unnecessary organic phase solution.
Dry 1h under film being placed in room temperature condition, is then placed on the constant temperature blast drying oven 2h of 60 DEG C by film.Gained film is named as MMM/PDNPs-0.3, represents that PDNPs filler is 0.3% relative to the mass percent of PEI.
Fig. 4 shows the contact angle on MMM/PDNPs-0.3 film surface; It is swelling and adsorb swelling that Fig. 5 and 6 respectively illustrates the area of MMM/PDNPs-0.3 film at room temperature in normal heptane, toluene, isopropyl alcohol and ethyl acetate four kinds of solvents; Fig. 7,8,9 and 10 respectively illustrates MMM/PDNPs-0.3 film at room temperature, both sides differential pressure of membrane be 4 and 10bar time normal heptane, toluene, isopropyl alcohol and ethyl acetate permeation flux; Figure 11 shows MMM/PDNPs-0.3 film at room temperature, and both sides differential pressure of membrane is 10bar, the cutoff performance curve of different molecular weight polyethylene glycol when solvent is isopropyl alcohol.
Embodiment 4
The method of embodiment 1 is adopted to prepare poly-dopamine powder of nanometric particles.
The polymine taking 4g50wt% is dissolved in 46g deionized water, fully stirs under room temperature, adds the Na of 0.05g subsequently
2cO
3gather dopamine powder of nanometric particles with 0.01g, at room temperature ultrasonic process 1h obtains solution A;
Taking 1g pyromellitic trimethylsilyl chloride is dissolved in 49g n-hexane, fully stirs 1h and obtain solution B under room temperature;
First be that the polyacrylonitrile ultrafiltration film surface submergence of 100kDa pours out deionized water after 30min in deionized water by molecule rejection.Subsequently solution A is coated in PAN film surface 10min, removes unnecessary aqueous phase solution.Finally B organic phase solution is coated in film surface 10min, and removes unnecessary organic phase solution.
Dry 1h under film being placed in room temperature condition, is then placed on the constant temperature blast drying oven 2h of 60 DEG C by film.Gained film is named as MMM/PDNPs-0.5, represents that PDNPs filler is 0.5% relative to the mass percent of PEI.
Fig. 2 and 3 respectively illustrates the stereoscan photograph of MMM/PDNPs-0.5 film surface and section; Fig. 4 shows the contact angle on MMM/PDNPs-0.5 film surface; It is swelling and adsorb swelling that Fig. 5 and 6 respectively illustrates the area of MMM/PDNPs-0.5 film at room temperature in normal heptane, toluene, isopropyl alcohol and ethyl acetate four kinds of solvents; Fig. 7,8,9 and 10 respectively illustrates MMM/PDNPs-0.5 film at room temperature, both sides differential pressure of membrane be 4 and 10bar time normal heptane, toluene, isopropyl alcohol and ethyl acetate permeation flux; Figure 11 shows MMM/PDNPs-0.5 film at room temperature, and both sides differential pressure of membrane is 10bar, the cutoff performance curve of different molecular weight polyethylene glycol when solvent is isopropyl alcohol.
comparative example:
The polymine taking 4g50wt% is dissolved in 46g deionized water, fully stirs under room temperature, adds the Na of 0.05g subsequently
2cO
3at room temperature ultrasonic process 1h;
Take 1g pyromellitic trimethylsilyl chloride to be dissolved in 49g n-hexane, under room temperature, fully stir 1h;
First the polyacrylonitrile ultrafiltration film surface submergence by molecule rejection being 100kDa, in deionized water after 30min, pours out deionized water.Subsequently aqueous phase solution is coated in PAN film surface 10min, removes unnecessary aqueous phase solution.Finally organic phase solution is coated in film surface 10min, and removes unnecessary organic phase solution.
Dry 1h under film being placed in room temperature condition, then film is placed on the constant temperature blast drying oven 2h of 60 DEG C, gained film is named as PAN/PEI.
Fig. 4 shows the contact angle on PAN/PEI film surface; It is swelling and adsorb swelling that Fig. 5 and 6 respectively illustrates the area of PAN/PEI film at room temperature in normal heptane, toluene, isopropyl alcohol and ethyl acetate four kinds of solvents; Fig. 7,8,9 and 10 respectively illustrates PAN/PEI film at room temperature, both sides differential pressure of membrane be 4 and 10bar time normal heptane, toluene, isopropyl alcohol and ethyl acetate permeation flux; Figure 11 shows PAN/PEI film at room temperature, and both sides differential pressure of membrane is 10bar, the cutoff performance curve of different molecular weight polyethylene glycol when solvent is isopropyl alcohol.
By the test of solvent resistance, as shown in Figure 5,6, prepared MMM/PDNPs-
xthe absorption of film is swelling and area is swelling is all less than blank film PAN/PEI, this may have good adhesion property due to poly-dopamine, can be adhered to each other closely by covalent bond and hydrogen bond with PEI segment, inhibit the motion of segment, enhance solvent resistance.In the test of solvent penetration flux, as shown in Fig. 7,8,9,10, except indivedual loading, (in Fig. 7,8, loading is 0.1; In Fig. 9,10, loading is 0.2), the flux of four kinds of solvents all reduces along with the increase of PDNPs loading, this may be due to the increase along with loading, and the PDNPs that mixed substrate membrane containing nano-grade molecular sieve adsorbs swelling and that area is swelling reduction and filling in four kinds of solvents suppresses the effect of sub-chain motion stronger caused.When in Fig. 7,8, loading is 0.1, the flux of normal heptane and toluene increases all to some extent relative to blank film, and possible cause is that the hydrophily on film surface reduces, and is conducive to the dissolving and the diffusion that improve the less solvent of polarity.When in Fig. 9,10, PDNPs loading is 0.2, increase when the permeation flux of isopropyl alcohol and ethyl acetate is 0.1 relative to loading, possible reason is that (1) improves the hydrophily on film surface, is conducive to the dissolving of polar molecule on the one hand along with the increase of dopamine ball loading; (2) add the number in the site forming hydrogen bond, by the impact of hydrogen bond action, be conducive to the diffusion of solvent molecule at cross-linked network.But then owing to adhering to each other with the form of covalent bond and hydrogen bond between PDNPs and PEI segment, inhibit the motion of segment.Therefore, under these two phase negative side combined influences, cause isopropyl alcohol and the permeation flux of ethyl acetate when loading is 0.2 to occur maximum.In cutoff performance test, as shown in figure 11, prepared MMM/PDNPs-
xthe molecular cut off of film is all less than blank film PAN/PEI, and along with the increase of loading, molecular cut off is less, this may be owing to adhering to each other with the effect of covalent bond and hydrogen bond between PDNPs and PEI segment, thus inhibit the motion of PEI segment, and effectively eliminate the non-selective hole of interface, improve rejection.By carrying out long-term stability test to MMM/PDNPs-0.1 film, as shown in figure 12, when the separating property of film reaches metastable state, at room temperature, both sides differential pressure of membrane is 10bar, and the permeation flux of isopropyl alcohol is 17.4Lm
-2s
-1, meanwhile, the rejection of film remains on 98.1%, shows outstanding separating property.
Claims (10)
1. a preparation method for solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve, is characterized in that, the polyacrylonitrile ultrafiltration film surface after fully absorbing water applies solution A and B solution successively, namely obtains described solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve after drying; Described solution A be poly-dopamine nanoparticulate dispersed in the aqueous phase solution of polymine, described B solution is the organic solution of pyromellitic trimethylsilyl chloride.
2. the preparation method of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve as claimed in claim 1, it is characterized in that, in described solution A, the mass ratio of polymine and poly-dopamine nano particle is 100:0.1-0.5; Polymine and Na
2cO
3mass ratio be 40:0.8-1.2; The mass ratio of polymine and deionized water is 1:23-25.
3. the preparation method of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve as claimed in claim 2, is characterized in that, during preparation solution A, is first fully dissolved in deionized water by polymine, adds Na subsequently under the condition stirred
2cO
3with poly-dopamine powder of nanometric particles, at room temperature ultrasonic process 0.5-1h.
4. the preparation method of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve as claimed in claim 1, it is characterized in that, described solution B is the solution that pyromellitic trimethylsilyl chloride is dissolved in n-hexane or normal heptane, and the mass concentration of pyromellitic trimethylsilyl chloride is 1-2%.
5. the preparation method of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve as claimed in claim 1, it is characterized in that, described polyacrylonitrile ultrafiltration film molecular cut off is 50-100kDa.
6. the preparation method of the solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve as described in as arbitrary in claim 1-5, is characterized in that, when coating A and B solution, respectively corresponding solution is coated in polyacrylonitrile ultrafiltration film surface 5-10min, then except the solution of striping excess surface.
7. the preparation method of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve as claimed in claim 6, it is characterized in that, described drying is prior to 1-2h dry under room temperature condition, then in 60 DEG C of dry 2-3h.
8. the solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve that the arbitrary described method of claim 1-7 is obtained, is characterized in that, in described film, poly-dopamine nano particle is 0.1-0.5% relative to the mass percent of polymine.
9. the application of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve described in claim 8, is characterized in that, described film is used for organic solvent nanofiltration.
10. the application of solvent resistant nanofiltration mixed substrate membrane containing nano-grade molecular sieve as claimed in claim 9, it is characterized in that, described organic solvent is normal heptane, toluene, isopropyl alcohol, ethyl acetate.
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| CN113181783A (en) * | 2021-07-01 | 2021-07-30 | 湖南澳维新材料技术有限公司 | Polyamide composite membrane and preparation method thereof |
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| YAFEI LI等: "Preparation of thin film composite nanofiltration membrane with improved structuralstability through the mediation of polydopamine", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106039998A (en) * | 2016-07-18 | 2016-10-26 | 浙江大学 | Beta-FeOOH nanocrystal-loaded photocatalytic composite nanofiltration membrane and preparation method thereof |
| CN106039998B (en) * | 2016-07-18 | 2019-02-05 | 浙江大学 | Load the photocatalysis composite nanometer filtering film and preparation method thereof of β-FeOOH nanocrystal |
| CN113181783A (en) * | 2021-07-01 | 2021-07-30 | 湖南澳维新材料技术有限公司 | Polyamide composite membrane and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN105536575B (en) | 2018-06-08 |
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