CN104841296A - Nanosized silica sphere/polypiperazine-amide nano composite nanofiltration membrane and preparation method thereof - Google Patents
Nanosized silica sphere/polypiperazine-amide nano composite nanofiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of water treatment membranes, and discloses a nanosized silica sphere/polypiperazine-amide nano composite nanofiltration membrane and a preparation method thereof. The nanosized silica sphere/polypiperazine-amide nano composite nanofiltration membrane is prepared by forming a polypiperazine-amide macromolecule functional separation layer embedded with nanosized silica spheres on an ultrafiltration support membrane. The nanosized silica spheres can be effectively introduced into the polypiperazine-amide macromolecule layer, so that the nano composite nanofiltration membrane with excellent properties can be prepared. Relatively strong oxygen bands are arranged between nanosized silica and polypiperazine-amide macromolecules of the nano composite nanofiltration membrane disclosed by the invention, so that the nanosized silica spheres can be uniformly and stably dispersed in the polypiperazine-amide macromolecule functional separation layer, the water flux of the nano composite nanofiltration membrane can be remarkably improved, good separation stability and membrane surface hydrophilicity are achieved, and meanwhile the nanosized silica sphere/polypiperazine-amide nano composite nanofiltration membrane is simple in preparation method, high in operability, low in production cost and good in industrial application prospect.
Description
Technical field
The invention belongs to membrane for water treatment technical field, be specifically related to a kind of nano combined NF membrane and preparation method thereof.
Background technology
Composite nanometer filtering film primarily of separating layer, supporting layer and nonwoven layer three part composition, wherein separating layer has been the functional layer of centrifugation.Polypiperazine-amide type composite nanometer filtering film can be applicable to the fields such as water demineralization, desalinization, Dye Removal, food processing and wastewater treatment, have broad application prospects, therefore this material causes the extensive concern of membrane material manufacturing enterprise and research institution.Polypiperazine-amide type composite nanometer filtering film usually with pyromellitic trimethylsilyl chloride and piperazine for primary raw material is obtained by interfacial polymerization.Interfacial polymerization is dissolved in by two kinds of very high for reactivity monomers in two kinds of immiscible solvents respectively, by generating the method for macromolecule member materials at two kinds of solvent interface polymerization reaction take places.Current the method is widely used in prepares composite nanometer filtering film and reverse osmosis membrane materials.
Nanosilica white sphere has nanometer size effect, Stability Analysis of Structures usually, size is controlled, pattern is regular, good hydrophilic property etc. advantage.Researcher finds nanosilica white sphere as additive, be introduced in the separating layer of aromatic polyamides reverse osmosis membrane in interfacial polymerization process, nano combined aromatic polyamides reverse osmosis membrane can be obtained, nanosilica white sphere is dispersed in aromatic polyamides separating layer, the method can significantly improve the water flux of aromatic polyamide composite reverse osmosis membrane, and its salt rejection rate is kept preferably simultaneously.Therefore, by being evenly spread to by nanosilica white sphere in composite membrane separating layer, improve the hydrophily on membrane material surface, the degree of cross linking simultaneously optimizing separating layer improves the effective ways of composite membrane water flux.But current the method is mainly used in the preparation of the nano combined reverse osmosis membrane of nanosilica white sphere/aromatic polyamides, also nanosilica white sphere is not incorporated into the relevant report in polypiperazine-amide nanofiltration membrane.In addition, in composite nanometer filtering film use procedure, still there is water flux problem on the low side, thus cause energy consumption and high expensive; Therefore, how to improve its water flux further keeps higher salt rejection rate to be one of emphasis of composite nanometer filtering film Study on Preparation Technology simultaneously always.
Summary of the invention
To be solved by this invention is the technical problem how improving composite nanometer filter membrane flux, nano combined NF membrane of a kind of high-throughout nanosilica white sphere/polypiperazine-amide and preparation method thereof is provided, contain the polypiperazine-amide function separating layer of nanosilica white sphere by interfacial polymerization at ultrafiltration support membrane surface formation one deck and obtain, because nanosilica white sphere surface is with abundant silicone hydroxyl functional group, between nanosilica white sphere and polypiperazine-amide separating layer, there is stronger hydrogen bond action, therefore Absorbable organic halogens is scattered in polypiperazine-amide separating layer, make this nano combined nanometer filtering film water flux high, stable performance, good hydrophilic property, salt rejection rate remains on higher level simultaneously, its preparation method process is simple simultaneously, workable, and preparation condition is easy to control, and has wide scale application prospect.
In order to solve the problems of the technologies described above, the present invention is achieved by following technical scheme:
The nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide, to form by interfacial polymerization the polypiperazine-amide complex function separating layer that one deck contains nanosilica white sphere and forms, specifically obtained by following preparation method on ultrafiltration support membrane surface:
(1) ultrafiltration support membrane is directly immersed in the aqueous phase solution containing piperazine and dodecyl sodium sulfate, dipping 0.5-20 minute, the aqueous phase solution that after taking out, removing described ultrafiltration support membrane surface is excessive; In described aqueous phase solution, the concentration of piperazine is 0.2-0.8w/v%, and the concentration of dodecyl sodium sulfate is 0.001-0.01w/v%; The pH value of described aqueous phase solution is 8-11;
(2) nanosilica white sphere and pyromellitic trimethylsilyl chloride to be joined in organic solvent and carry out ultrasonic disperse 30-60 minute and be mixed with uniform oil-phase solution; The concentration of nanosilica white sphere described in described oil-phase solution is 0.03-0.09w/v%, and described nanosilica white sphere is of a size of 20-300 nanometer, and the concentration of described pyromellitic trimethylsilyl chloride is 0.2-0.8w/v%;
Again the ultrafiltration support membrane that step (1) obtains is immersed in described oil-phase solution and carries out interface polymerization reaction, reaction time is 0.5-20 minute, thus the polypiperazine-amide Motor cortex of nanosilica white sphere is contained at ultrafiltration support membrane Surface Creation one deck, form the nano combined NF membrane of nascent state;
(3) oil-phase solution that after taking out, the described nascent state of removing nano combined NF membrane surface is excessive, heat-treat, heat treatment temperature is 60-95 DEG C, and heat treatment time is 3-30 minute, can obtain the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide with deionized water rinsing.
Wherein, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or the polyether sulfone ultrafiltration support membrane of aperture 40-100 nanometer.
Wherein, the pH value sodium phosphate of described aqueous phase solution, sodium hydrogen phosphate or triethylamine regulate.
Wherein, the organic solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
Preferably, described in the described aqueous phase solution of step (1), the concentration of piperazine is 0.2w/v%; Described in the described oil-phase solution of step (2), the concentration of nanosilica white sphere is 0.06w/v%, and the concentration of described pyromellitic trimethylsilyl chloride is 0.2w/v%.
A preparation method for the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, the method is carried out according to following steps:
(1) ultrafiltration support membrane is directly immersed in the aqueous phase solution containing piperazine and dodecyl sodium sulfate, dipping 0.5-20 minute, the aqueous phase solution that after taking out, removing described ultrafiltration support membrane surface is excessive; In described aqueous phase solution, the concentration of piperazine is 0.2-0.8w/v%, and the concentration of dodecyl sodium sulfate is 0.001-0.01w/v%; The pH value of described aqueous phase solution is 8-11;
(2) nanosilica white sphere and pyromellitic trimethylsilyl chloride to be joined in organic solvent and carry out ultrasonic disperse 30-60 minute and be mixed with uniform oil-phase solution; The concentration of nanosilica white sphere described in described oil-phase solution is 0.03-0.09w/v%, and described nanosilica white sphere is of a size of 20-300 nanometer, and the concentration of described pyromellitic trimethylsilyl chloride is 0.2-0.8w/v%;
Again the polysulfones ultrafiltration support membrane that step (1) obtains is immersed in described oil-phase solution and carries out interface polymerization reaction, reaction time is 0.5-20 minute, thus the polypiperazine-amide Motor cortex of nanosilica white sphere is contained at ultrafiltration support membrane Surface Creation one deck, form the nano combined NF membrane of nascent state;
(3) oil-phase solution that after taking out, the described nascent state of removing nano combined NF membrane surface is excessive, heat-treat, heat treatment temperature is 60-95 DEG C, and heat treatment time is 3-30 minute, can obtain the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide with deionized water rinsing.
Wherein, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or the polyether sulfone ultrafiltration support membrane of aperture 40-100 nanometer.
Wherein, the pH value sodium phosphate of described aqueous phase solution, sodium hydrogen phosphate or triethylamine regulate.
Wherein, the organic solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
Preferably, described in the described aqueous phase solution of step (1), the concentration of piperazine is 0.2w/v%; Described in the described oil-phase solution of step (2), the concentration of nanosilica white sphere is 0.06w/v%, and the concentration of described pyromellitic trimethylsilyl chloride is 0.2w/v%.
The invention has the beneficial effects as follows:
Nanosilica white sphere is incorporated in polypiperazine-amide separating layer by interfacial polymerization by the present invention, owing to having carried out ultrasonic disperse process to the oil-phase solution containing nanosilica white sphere and pyromellitic trimethylsilyl chloride in preparation process, nanosilica white sphere can be dispersed in the polypiperazine-amide separating layer of nano combined NF membrane; In addition, owing to having stronger hydrogen bond action between the silicone hydroxyl on nanosilica white sphere surface and the amido link of polypiperazine-amide, the nanosilica white sphere formed/polypiperazine-amide Stability Analysis of Structures, has stable separating property simultaneously.
The nano combined NF membrane of nanosilica white sphere/polypiperazine-amide prepared by the present invention, because nanosilica white sphere has stronger hydrophily, is introduced in polypiperazine-amide separating layer, and the overall hydrophily of nano combined NF membrane can be made to be improved significantly; Hydrophilic raising enhances the active force of film surface and hydrone simultaneously, thus improves the water flux of the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide.In addition, nanosilica white sphere be introduced in the degree of cross linking reducing polypiperazine-amide separating layer to a certain extent, this is also conducive to the raising of water flux.
Experiment shows, under the test condition of 2000mg/L Adlerika, 0.5MPa test pressure and 25 DEG C of solution temperatures, the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide prepared by the present invention, its water flux can reach 10.23 ~ 51.34L/m
2h, salt rejection rate can reach 68.23 ~ 92.34%.When the present invention takes the concentration of piperazine to be 0.2w/v%, nanosilica white sphere concentration is 0.06w/v%, when the concentration of pyromellitic trimethylsilyl chloride is 0.2w/v%, water flux 1.45 times of pure polypiperazine-amide nanofiltration membrane under being about identical preparation condition, and salt rejection rate still can remain on higher level.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail:
Following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.
Embodiment 1:
(1) in deionized water, a certain amount of piperazine monomer is added, its concentration is made to reach 0.2w/v%, a certain amount of dodecyl sodium sulfate is added again in this solution, make its concentration reach 0.005w/v%, and then with sodium phosphate, the pH value of above-mentioned solution is adjusted to 10, mix formation aqueous phase solution, be that the polysulfones ultrafiltration support membrane of 60 nanometers is immersed in this aqueous phase solution again by aperture, flood 2 minutes, then polysulfones ultrafiltration support membrane is taken out, remove the aqueous phase solution of its excess surface.
(2) pyromellitic trimethylsilyl chloride is joined in Isopar G type hydrocarbon mixture, be mixed with the oil-phase solution of 0.2w/v%, adding the nanosilica white sphere being of a size of 230 nanometers more wherein makes its concentration reach 0.06w/v%, and within 40 minutes, forms uniform oil-phase solution by ultrasonic process; Again the polysulfones ultrafiltration support membrane that step (1) obtains is immersed in this oil-phase solution, reacts 0.5 minute, after taking-up, remove the oil-phase solution of film excess surface; Thus the polypiperazine-amide Motor cortex of nanosilica white sphere is contained at ultrafiltration support membrane Surface Creation one deck, form the nano combined NF membrane of nascent state.
(3) by the nano combined NF membrane of nascent state that obtains 80 DEG C of baking oven interior heats process 5 minutes, then taking-up with deionized water rinsing for several times, obtain the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide.
Embodiment 2:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the dip time of polysulfones ultrafiltration support membrane in aqueous phase solution is 0.5 minute.
Embodiment 3:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the dip time of polysulfones ultrafiltration support membrane in aqueous phase solution is 20 minutes.
Embodiment 4:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the concentration of piperazine is 0.6w/v%.
Embodiment 5:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the concentration of piperazine is 0.8w/v%.
Embodiment 6:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the concentration of dodecyl sodium sulfate is 0.001w/v%.
Embodiment 7:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the concentration of dodecyl sodium sulfate is 0.01w/v%.
Embodiment 8:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the reaction time in oil-phase solution is 2 minutes.
Embodiment 9:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the reaction time in oil-phase solution changes 20 minutes into.
Embodiment 10:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the concentration of nanosilica white sphere is 0.03w/v%.
Embodiment 11:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the concentration of nanosilica white sphere is 0.09w/v%.
Embodiment 12:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that nanosilica white sphere is of a size of 20 nanometers.
Embodiment 13:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that nanosilica white sphere is of a size of 300 nanometers.
Embodiment 14:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the concentration of pyromellitic trimethylsilyl chloride is 0.6w/v%.
Embodiment 15:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the concentration of pyromellitic trimethylsilyl chloride is 0.8w/v%.
Embodiment 16:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that heat treatment temperature is 60 DEG C
Embodiment 17:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that heat treatment temperature is 95 DEG C.
Embodiment 18:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that heat treatment time is 3 minutes.
Embodiment 19:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that heat treatment time is 30 minutes.
Embodiment 20:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the aperture of polysulfones ultrafiltration support membrane is 40 nanometers.
Embodiment 21:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the aperture of polysulfones ultrafiltration support membrane is 100 nanometers.
Embodiment 22:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that ultrafiltration support membrane selects the polyether sulfone ultrafiltration support membrane of aperture 60 nanometer.
Embodiment 23:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only, with sodium phosphate, pH value is adjusted to 8.
Embodiment 24:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only, with sodium phosphate, pH value is adjusted to 11.
Embodiment 25:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only, with sodium hydrogen phosphate, pH value is adjusted to 10.
Embodiment 26:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only, with triethylamine, pH value is adjusted to 10.
Embodiment 27:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the organic solvent in oil-phase solution is normal hexane.
Embodiment 28:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the organic solvent in oil-phase solution is normal heptane.
Embodiment 29:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the time of ultrasonic process is 30 minutes.
Embodiment 30:
Adopt the method for embodiment 1 to prepare the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, its difference is only that the time of ultrasonic process is 60 minutes.
Embodiment 31:
For showing the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide prepared by the present invention and the difference of pure polypiperazine-amide composite nanometer filtering film in separating property, adopt the method for embodiment 1 to prepare pure polypiperazine-amide composite nanometer filtering film, its difference is only not add nanosilica white sphere.
NF membrane the various embodiments described above prepared is kept in water, and test its water flux and salt rejection rate under 2000mg/L Adlerika, 0.5MPa test pressure and 25 DEG C of solution temperatures, test result is in table 1.
The separating property parameter of NF membrane under the different preparation condition of table 1
| Embodiment | Water flux (L/m 2h) | Salt rejection rate (%) |
| 1 | 28.07 | 83.56 |
| 2 | 51.34 | 68.23 |
| 3 | 15.32 | 89.63 |
| 4 | 23.69 | 85.61 |
| 5 | 21.23 | 86.93 |
| 6 | 25.56 | 81.78 |
| 7 | 26.54 | 82.74 |
| 8 | 22.79 | 89.23 |
| 9 | 10.23 | 92.34 |
| 10 | 22.65 | 89.81 |
| 11 | 32.34 | 75.47 |
| 12 | 24.32 | 84.58 |
| 13 | 31.34 | 80.28 |
| 14 | 21.34 | 86.56 |
| 15 | 16.80 | 90.96 |
| 16 | 35.21 | 79.78 |
| 17 | 26.44 | 84.39 |
| 18 | 28.79 | 82.94 |
| 19 | 24.20 | 84.32 |
| 20 | 25.11 | 84.02 |
| 21 | 30.21 | 81.53 |
| 22 | 27.87 | 83.32 |
| 23 | 38.46 | 75.63 |
| 24 | 39.32 | 71.18 |
| 25 | 26.43 | 80.89 |
| 26 | 23.40 | 82.37 |
| 27 | 26.43 | 82.19 |
| 28 | 25.16 | 83.60 |
| 29 | 31.30 | 72.68 |
| 30 | 23.77 | 83.35 |
| 31 | 19.36 | 94.58 |
Result shows, piperazine, pyromellitic trimethylsilyl chloride and nanosilica white sphere concentration all have material impact to the separating property of the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide; With the increase of piperazine and pyromellitic trimethylsilyl chloride concentration, the salt rejection rate of gained NF membrane increases gradually, and water flux reduces gradually; With the increase of nanosilica white sphere concentration, the salt rejection rate of gained NF membrane reduces gradually, and water flux increases gradually; Be 0.2w/v% in piperazine concentration, pyromellitic trimethylsilyl chloride is 0.2w/v%, and when nanosilica white sphere concentration is 0.06w/v%, the separating property of the nano combined NF membrane of gained nanosilica white sphere/polypiperazine-amide is optimized the most.In addition, time of the concentration of pH value, pH value regulator kind, dodecyl sodium sulfate, ultrafiltration support membrane kind and aperture, oil phase solvent kind, dip time, the reaction time in oil phase, ultrasonic process in aqueous phase and heat treatment temperature and time also have a certain impact to the separating property tool of the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide.Compared with the pure polypiperazine-amide composite nanometer filtering film obtained under identical preparation condition, the separating property of this nano combined NF membrane significantly improves, and its water flux is about 1.45 times of pure polypiperazine-amide composite nanometer filtering film, and salt rejection rate still can remain on higher level.
Claims (10)
1. the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, it is characterized in that, form on ultrafiltration support membrane surface the polypiperazine-amide complex function separating layer that one deck contains nanosilica white sphere by interfacial polymerization to form, specifically obtained by following preparation method:
(1) ultrafiltration support membrane is directly immersed in the aqueous phase solution containing piperazine and dodecyl sodium sulfate, dipping 0.5-20 minute, the aqueous phase solution that after taking out, removing described ultrafiltration support membrane surface is excessive; In described aqueous phase solution, the concentration of piperazine is 0.2-0.8w/v%, and the concentration of dodecyl sodium sulfate is 0.001-0.01w/v%; The pH value of described aqueous phase solution is 8-11;
(2) nanosilica white sphere and pyromellitic trimethylsilyl chloride to be joined in organic solvent and carry out ultrasonic disperse 30-60 minute and be mixed with uniform oil-phase solution; The concentration of nanosilica white sphere described in described oil-phase solution is 0.03-0.09w/v%, and described nanosilica white sphere is of a size of 20-300 nanometer, and the concentration of described pyromellitic trimethylsilyl chloride is 0.2-0.8w/v%;
Again the ultrafiltration support membrane that step (1) obtains is immersed in described oil-phase solution and carries out interface polymerization reaction, reaction time is 0.5-20 minute, thus the polypiperazine-amide Motor cortex of nanosilica white sphere is contained at ultrafiltration support membrane Surface Creation one deck, form the nano combined NF membrane of nascent state;
(3) oil-phase solution that after taking out, the described nascent state of removing nano combined NF membrane surface is excessive, heat-treat, heat treatment temperature is 60-95 DEG C, and heat treatment time is 3-30 minute, can obtain the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide with deionized water rinsing.
2. the nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide according to claim 1, is characterized in that, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or the polyether sulfone ultrafiltration support membrane of aperture 40-100 nanometer.
3. the nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide according to claim 1, is characterized in that, the pH value sodium phosphate of described aqueous phase solution, sodium hydrogen phosphate or triethylamine regulate.
4. the nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide according to claim 1, is characterized in that, the organic solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
5. the nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide according to claim 1, is characterized in that, described in the described aqueous phase solution of step (1), the concentration of piperazine is 0.2w/v%; Described in the described oil-phase solution of step (2), the concentration of nanosilica white sphere is 0.06w/v%, and the concentration of described pyromellitic trimethylsilyl chloride is 0.2w/v%.
6. a preparation method for the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide, is characterized in that, the method is carried out according to following steps:
(1) ultrafiltration support membrane is directly immersed in the aqueous phase solution containing piperazine and dodecyl sodium sulfate, dipping 0.5-20 minute, the aqueous phase solution that after taking out, removing described ultrafiltration support membrane surface is excessive; In described aqueous phase solution, the concentration of piperazine is 0.2-0.8w/v%, and the concentration of dodecyl sodium sulfate is 0.001-0.01w/v%; The pH value of described aqueous phase solution is 8-11;
(2) nanosilica white sphere and pyromellitic trimethylsilyl chloride to be joined in organic solvent and carry out ultrasonic disperse 30-60 minute and be mixed with uniform oil-phase solution; The concentration of nanosilica white sphere described in described oil-phase solution is 0.03-0.09w/v%, and described nanosilica white sphere is of a size of 20-300 nanometer, and the concentration of described pyromellitic trimethylsilyl chloride is 0.2-0.8w/v%;
Again the polysulfones ultrafiltration support membrane that step (1) obtains is immersed in described oil-phase solution and carries out interface polymerization reaction, reaction time is 0.5-20 minute, thus the polypiperazine-amide Motor cortex of nanosilica white sphere is contained at ultrafiltration support membrane Surface Creation one deck, form the nano combined NF membrane of nascent state;
(3) oil-phase solution that after taking out, the described nascent state of removing nano combined NF membrane surface is excessive, heat-treat, heat treatment temperature is 60-95 DEG C, and heat treatment time is 3-30 minute, can obtain the nano combined NF membrane of nanosilica white sphere/polypiperazine-amide with deionized water rinsing.
7. the preparation method of the nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide according to claim 6, is characterized in that, described ultrafiltration support membrane is polysulfones ultrafiltration support membrane or the polyether sulfone ultrafiltration support membrane of aperture 40-100 nanometer.
8. the preparation method of the nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide according to claim 6, is characterized in that, the pH value sodium phosphate of described aqueous phase solution, sodium hydrogen phosphate or triethylamine regulate.
9. the preparation method of the nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide according to claim 6, is characterized in that, the organic solvent in described oil-phase solution is Isopar G type hydrocarbon mixture, normal hexane or normal heptane.
10. the preparation method of the nano combined NF membrane of a kind of nanosilica white sphere/polypiperazine-amide according to claim 6, is characterized in that, described in the described aqueous phase solution of step (1), the concentration of piperazine is 0.2w/v%; Described in the described oil-phase solution of step (2), the concentration of nanosilica white sphere is 0.06w/v%, and the concentration of described pyromellitic trimethylsilyl chloride is 0.2w/v%.
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| CN109224864A (en) * | 2018-09-12 | 2019-01-18 | 广东产品质量监督检验研究院 | A kind of dark color textiles and leathers extract liquor decoloration novel process for pretreating |
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| CN106215726A (en) * | 2016-08-08 | 2016-12-14 | 贵阳时代沃顿科技有限公司 | A kind of siliceous solvent resistant NF membrane and preparation method thereof |
| CN106215726B (en) * | 2016-08-08 | 2019-02-15 | 时代沃顿科技有限公司 | A kind of siliceous solvent resistant nanofiltration membrane and preparation method thereof |
| CN108970425A (en) * | 2018-08-23 | 2018-12-11 | 师帅帅 | A kind of high-salt wastewater processing polymer film and preparation method thereof |
| CN109224864A (en) * | 2018-09-12 | 2019-01-18 | 广东产品质量监督检验研究院 | A kind of dark color textiles and leathers extract liquor decoloration novel process for pretreating |
| CN109224864B (en) * | 2018-09-12 | 2021-02-19 | 广东产品质量监督检验研究院 | Novel process for decoloring dark textile and leather extract liquor |
| CN109675449A (en) * | 2019-01-10 | 2019-04-26 | 自然资源部天津海水淡化与综合利用研究所 | The preparation method of the extremely low pressure aromatic polyamide base complex reverse osmosis membrane of high separability energy |
| CN112023731A (en) * | 2019-07-01 | 2020-12-04 | 江苏久吾高科技股份有限公司 | Preparation method of high-flux low-pressure reverse osmosis membrane |
| WO2023084369A1 (en) * | 2021-11-12 | 2023-05-19 | 3M Innovative Properties Company | Method of processing polynucleic acids |
| WO2023084370A1 (en) * | 2021-11-12 | 2023-05-19 | 3M Innovative Properties Company | Solid support comprising ligands suitable for polynucleic acid processing, articles and methods |
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