CN105903359A - Chitosan functionalized graphene oxide/polyvinylidene fluoride hybrid ultrafiltration membrane and preparation method thereof - Google Patents
Chitosan functionalized graphene oxide/polyvinylidene fluoride hybrid ultrafiltration membrane and preparation method thereof Download PDFInfo
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- CN105903359A CN105903359A CN201610396809.XA CN201610396809A CN105903359A CN 105903359 A CN105903359 A CN 105903359A CN 201610396809 A CN201610396809 A CN 201610396809A CN 105903359 A CN105903359 A CN 105903359A
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- graphene oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/74—Natural macromolecular material or derivatives thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/28—Degradation or stability over time
Abstract
The invention provides a chitosan functionalized graphene oxide/polyvinylidene fluoride hybrid ultrafiltration membrane and a preparation method thereof. Firstly, chitosan is used for covalent functionalization of graphene oxide to prepare chitosan-graphene oxide; the chitosan-graphene oxide is dispersed in an organic solvent in an ultrasonic mode, then polyvinylidene fluoride and a pore-foaming agent are added and stirred at certain temperature to be evenly dissolved to obtain a membrane casting solution, water serves as a coagulating bath, and the chitosan-graphene oxide/polyvinylidene fluoride hybrid ultrafiltration membrane is prepared through the immerged phase-inversion process. The chitosan-graphene oxide/polyvinylidene fluoride hybrid ultrafiltration membrane prepared through the method improves dispersibility of graphene oxide in a membrane matrix, and compared with a graphene oxide/polyvinylidene fluoride ultrafiltration membrane, hydrophilicity, water flux, antifouling property and other aspects are greatly improved.
Description
Technical field
The invention belongs to Ultra filtration membrane technical field, be specifically related to a kind of chitosan functional graphene oxide/Kynoar miscellaneous
Change ultrafilter membrane and preparation method thereof.
Background technology
Kynoar because of its good filming performance, such as good mechanical performance, high temperature resistant and chemical resistance etc., extensively should
For preparing ultrafilter membrane.But because Kynoar itself is a kind of hydrophobic polymer, the polyvinylidene fluoride (PVDF) ultrafiltration membrane of preparation is hydrophilic
Property is poor, causes water flux low, and in filter process, pollutant easily adsorb and are deposited on film surface or fenestra, make membrance separation
Can significantly decline, this most seriously constrains ultrafilter membrane application industrially.
Improve the hydrophilic of polyvinylidene fluoride (PVDF) ultrafiltration membrane and carry out the separating property of reinforcing membrane and antifouling property is current Ultra filtration membrane neck
The focus of territory research.Blending and modifying is modifying agent to be directly mixed with in casting solution prepare hybridized film, because it is simple to operate, and application
Scope is wide, is a kind of modal membrane modifying method.Recent years, owing to graphene oxide contains abundant hydrophilic radical,
Such as carboxyl, hydroxyl and epoxy radicals, it is used in a large number by people polyvinylidene fluoride (PVDF) ultrafiltration membrane is carried out hydrophilic modifying.Change by being blended
The method of property is directly added into graphene oxide in casting solution and is prepared for graphene oxide/Kynoar hybrid membranes.Preparation
Graphene oxide/Kynoar hybrid membranes compares pure polyvinylidene fluoride (PVDF) ultrafiltration membrane at hydrophilic, water flux and antipollution etc.
Film properties aspect is obviously improved.But owing to the π-πconjugation of graphene oxide sheet interlayer makes graphene oxide special
Easily assembling, cause graphene oxide to disperse in Kynoar membrane matrix the most uneven, how in coherent condition, this just makes
Obtain graphene oxide for improving the hydrophilic of polyvinylidene fluoride (PVDF) ultrafiltration membrane by serious constraint.
Summary of the invention
The invention aims to improve graphene oxide dispersibility in polyvinylidene fluoride (PVDF) ultrafiltration membrane substrate, make graphite oxide
Alkene strongly hydrophilic gives full play of, and promotes graphene oxide/polyvinylidene fluoride (PVDF) ultrafiltration membrane performance, it is provided that a kind of chitosan function
Changing graphene oxide/Kynoar hybrid membranes and preparation method thereof, this preparation method is simple, the hybrid membranes prepared
Can be excellent.
For achieving the above object, the present invention adopts the following technical scheme that:
A kind of chitosan functional graphene oxide/Kynoar hybrid membranes, by weight percentage, the raw material bag of ultrafilter membrane
Include Kynoar 16-20%, porogen 0.3-5%, organic solvent 78-82% and chitosan-graphene oxide；Wherein, shell gathers
Sugar-graphene oxide weight is the 0.2-2% of Kynoar weight.
The present invention is further improved by, described Kynoar the most in advance in vacuum drying oven 110 DEG C be dried
10-15h。
The present invention is further improved by, and described porogen is in polyvinylpyrrolidone, Polyethylene Glycol, polyvinyl alcohol
Kind.
The present invention is further improved by, and described organic solvent is dimethylformamide, dimethyl acetylamide, N-methylpyrrole
One in alkanone, dimethyl sulfoxide.
The present invention is further improved by, and described chitosan-graphene oxide is laminar structured, and thickness is 2-3nm.
The preparation method of a kind of chitosan functional graphene oxide/Kynoar hybrid membranes, comprises the following steps:
Chitosan-graphene oxide is added in organic solvent, ultrasonic under room temperature after, obtain chitosan-graphene oxide dispersion；
Adding Kynoar and porogen in chitosan-graphene oxide dispersion, stirring and dissolving is uniform, and standing and defoaming is cast
Film liquid, then scrapes on polyester non-woven fabric equably by casting solution, forms cast layer, immerse the most at once on polyester non-woven fabric
In coagulating bath, after film forming to be solidified, film is peeled off, continue to soak in deionized water, the solvent that abjection is remaining, obtain shell and gather
Sugar functional graphene oxide/Kynoar hybrid membranes；Wherein, by weight percentage, Kynoar is 16-20%,
Porogen is 0.3-5%, and organic solvent is 78-82%, and chitosan-graphene oxide weight is the 0.2-2% of Kynoar weight.
The present invention is further improved by, and described chitosan-graphene oxide prepares by the following method:
Chitosan is dissolved in the glacial acetic acid solution that volume fraction is 1-3%, is configured to the chitosan glacial acetic acid of mass fraction 1-3%
Solution；
Adding graphene oxide in deionized water, under room temperature, ultrasonic 1h, obtains graphene oxide dispersion；Under agitation by oxygen
Functionalized graphene dispersion liquid joins in chitosan glacial acetic acid solution, uses glacial acetic acid centrifuge washing for several times, move under room temperature after stirring 24h
Except unreacted chitosan, the most again with deionized water centrifuge washing the most for several times, vacuum drying, prepare chitosan-graphene oxide；
Wherein, graphene oxide is 1:10 with the mass ratio of chitosan；Gained chitosan-graphene oxide is laminar structured, and thickness is
2-3nm。
The present invention is further improved by, and described ultrasonic time is 1h, and the temperature of stirring is 40-60 DEG C, and the time of stirring is
24-36h；The temperature of described standing and defoaming is 40-60 DEG C, and the time of standing and defoaming is 12-24h.
The present invention is further improved by, and described coagulating bath is deionized water, and water temperature is 20-30 DEG C；In described immersion coagulating bath
Time be 15-20min；Described porogen is the one in polyvinylpyrrolidone, Polyethylene Glycol, polyvinyl alcohol；Described have
Machine solvent is the one in dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide.
The present invention is further improved by, and described cast layer thickness is 130-180 μm；Described immersion in deionized water time
Between be 24-48h.
Compared with prior art, the invention have the benefit that
The present invention in organic solvent, adds Kynoar and porogen in necessarily chitosan-graphene oxide ultrasonic disperse
At a temperature of stirring and dissolving uniformly obtain casting solution, with water as coagulating bath, use immersion precipitation phase inversion process prepare chitosan-
Graphene oxide/Kynoar hybrid membranes.It is critical only that of the present invention utilizes chitosan that graphene oxide is carried out covalency merit
Energyization, improves graphene oxide dispersibility in Kynoar membrane matrix, makes graphene oxide/polyvinylidene fluoride (PVDF) ultrafiltration membrane
Can promote further.Preparation method of the present invention is simple, and the hybrid membranes excellent performance obtained preferably solves graphite oxide
Alkene rendezvous problem in Kynoar membrane matrix.
The film that the method obtains compared with the polyvinylidene fluoride film filling non-functional graphene oxide, hydrophilic, water flux and
The aspects such as antipollution are all obviously improved.
Further, doing porogen at polyvinylpyrrolidone, dimethyl acetylamide does organic solvent, chitosan-graphene oxide
In the case of addition is 0.6%, the chitosan functional graphene oxide/Kynoar hybrid membranes obtained and graphite oxide
Alkene/Kynoar hybrid membranes is compared, and the water contact angle of film is dropped to 64.2 ° by 73.9 °；The pure water flux of film by
576.92L/m2H rises to 737.18L/m2h；The flux recovery rate of film is risen to 69.57% by 63.89%, the BSA flux of film
Attenuation rate is reduced to 79.3% by 83.29%.
Detailed description of the invention
Illustrate how to prepare chitosan functional graphene oxide/Kynoar hydridization ultrafiltration below in conjunction with specific embodiment
Film, and the performance of prepared film.
In following example, Kynoar is purchased from Renault SA of the U.S., and model is Su Wei-1015；Graphene oxide is purchased from south
Capital pioneer's nanosecond science and technology company limited.
Embodiment 1
1) weigh 3g chitosan to be dissolved in the glacial acetic acid solution that 147g volume fraction is 2% and be made into shell that mass fraction is 2% and gather
Sugar glacial acetic acid solution, then 0.3g graphene oxide is added in deionized water, ultrasonic 1h under room temperature, obtain uniform graphite oxide
Alkene dispersion liquid；
In the case of stirring, graphene oxide dispersion is added drop-wise at leisure in chitosan glacial acetic acid solution above, under room temperature
Stirring 24h, reaction terminate after with glacial acetic acid centrifuge washing for several times, remove unreacted chitosan, the most again with deionized water from
The heart washs for several times, is vacuum dried 24h, prepares chitosan-graphene oxide at 60 DEG C, and chitosan-graphene oxide is nano combined
Thing.
2) join casting solution 30g: weigh 0.036g chitosan-graphene oxide, add 23.064g dimethyl acetylamide, under room temperature
Ultrasonic 1h, obtains uniform chitosan-graphene oxide dispersion；
Weigh 6g Kynoar (being vacuum dried 12h at 110 DEG C before using), 0.9g polyvinylpyrrolidone (molecular weight successively
58000g/mol) join in chitosan-graphene oxide dispersion above, at 60 DEG C, stir 24h, constant temperature at 60 DEG C
Standing and defoaming 12h, obtains casting solution, is then scraped equably on polyester non-woven fabric by casting solution scraper, forms cast layer,
Cast layer thickness is 150 ± 10 μm, puts in the deionized water of 25 DEG C the most at once, after 15min, film is peeled off from glass plate,
Continue to soak 48h in deionized water, make residual solvent removing completely, prepare chitosan functional graphene oxide/polyvinylidene fluoride
Alkene hybrid membranes.
Reference examples 1
Difference with embodiment 1 is, add in casting solution is the graphene oxide without functionalization.Concrete operations are as follows:
Joining casting solution 30g, weigh 0.036g graphene oxide, add 23.064g dimethyl acetylamide, under room temperature, ultrasonic 1h, obtains
The uniform dispersion of graphene oxide；Weigh 6g Kynoar (110 DEG C of vacuum drying 12h), 0.9g polyvinyl pyrrole successively
Alkanone (molecular weight 58000g/mol) adds in graphene oxide dispersion above, and 60 DEG C of stirring 24h, then at 60 DEG C of constant temperature
Standing and defoaming 12h, scrapes on polyester non-woven fabric equably with scraper, forms cast layer, and cast layer thickness is 150 ± 10 μm, so
After put at once in the deionized water of 25 DEG C, after 15min, film is peeled off from glass plate, continues to soak 48h in deionized water,
Make residual solvent removing completely, prepare graphene oxide/Kynoar hybrid membranes.
Reference examples 2
Difference with embodiment 1 is, does not adds chitosan-graphene oxide in casting solution.Concrete operations are as follows: join casting solution
30g, weighs 6g Kynoar (being vacuum dried 12h at 110 DEG C before using), 0.9g polyvinylpyrrolidone (molecule successively
Amount 58000g/mol) add 23.1g dimethyl acetylamide in, 60 DEG C stirring 24h, then at 60 DEG C of constant temperature standing and defoaming 12h,
Scraping equably on polyester non-woven fabric with scraper, form cast layer, cast layer thickness is 150 ± 10 μm, puts into 25 DEG C the most at once
Deionized water in, after 15min, film is peeled off from glass plate, continues to soak 48h in deionized water, make residual solvent remove
Completely, pure polyvinylidene fluoride (PVDF) ultrafiltration membrane is prepared.
Using water contact angle measuring instrument to measure the hydrophilic of obtained film, the water measuring film with dead end agitator tank defecator leads to
Amount, flux recovery rate and attenuation rate, the results are shown in Table 1.
The Performance comparision of 1 three kinds of different films of table
As can be seen from Table 1, the hydrophilic of polyvinylidene fluoride (PVDF) ultrafiltration membrane of chitosan functional graphene oxide, water flux are added
And the property such as antipollution compares and directly fills the polyvinylidene fluoride (PVDF) ultrafiltration membrane of graphene oxide and have more significant enhancing.
Embodiment 2
1) preparation of chitosan-stannic oxide/graphene nano composite is identical with embodiment 1.
2) difference with embodiment 1 is, the chitosan added in casting solution-graphene oxide amount is different.Concrete operations are such as
Under: join casting solution 30g, weigh 0.018g chitosan-graphene oxide, add 23.082g dimethyl acetylamide, super under room temperature
Sound 1h, obtains uniform chitosan-graphene oxide dispersion；
Weigh 6g Kynoar (110 DEG C of vacuum drying 12h), 0.9g polyvinylpyrrolidone (molecular weight 58000g/mol) successively
Join in chitosan-graphene oxide dispersion above, stirring 24h at 60 DEG C, constant temperature standing and defoaming 12h at 60 DEG C,
Scraping equably on polyester non-woven fabric with scraper, form cast layer, cast layer thickness is 150 ± 10 μm, puts into 25 DEG C the most at once
Deionized water in, after 15min, film is peeled off from glass plate, continues to soak 48h in deionized water, make residual solvent remove
Completely, chitosan functional graphene oxide/Kynoar hybrid membranes is prepared.
Obtained film, measuring its water contact angle is 71.35 °, and water flux is 673.08L/m2H, flux recovery rate is 66.53%,
Attenuation rate is 82.04%.Film properties is had an impact by the content the most relatively understanding chitosan-graphene oxide.
Chitosan-graphene oxide is added in organic solvent, ultrasonic under room temperature after, obtain chitosan-graphene oxide dispersion；To
Adding Kynoar and porogen in chitosan-graphene oxide dispersion, stirring and dissolving is uniform, and standing and defoaming obtains casting film
Liquid, then scrapes on polyester non-woven fabric equably by casting solution, forms cast layer, immerse solidifying the most at once on polyester non-woven fabric
Gu in Yu, after film forming to be solidified, film is peeled off, continue to soak in deionized water, the solvent that abjection is remaining, obtain chitosan
Functional graphene oxide/Kynoar hybrid membranes.
Embodiment 3
1) preparation of chitosan-graphene oxide:
Chitosan is dissolved in the glacial acetic acid solution that volume fraction is 1%, is configured to the chitosan glacial acetic acid solution of mass fraction 3%；
Adding graphene oxide in deionized water, under room temperature, ultrasonic 1h, obtains graphene oxide dispersion；Under agitation by oxygen
Functionalized graphene dispersion liquid joins in chitosan glacial acetic acid solution, uses glacial acetic acid centrifuge washing for several times, move under room temperature after stirring 24h
Except unreacted chitosan, the most again with deionized water centrifuge washing the most for several times, vacuum drying, prepare chitosan-graphene oxide；
Wherein, graphene oxide is 1:10 with the mass ratio of chitosan；Gained chitosan-graphene oxide is laminar structured, and thickness is
2-3nm。
2) chitosan-graphene oxide is added in organic solvent, under room temperature after ultrasonic 1h, obtain chitosan-graphene oxide
Dispersion liquid；Add in chitosan-graphene oxide dispersion Kynoar (before Shi Yonging 110 DEG C vacuum drying 15h) and
Porogen, stirs 36h, standing and defoaming 24h at 40 DEG C at 40 DEG C, obtains casting solution, then scraped equably by casting solution
On polyester non-woven fabric, polyester non-woven fabric is formed cast layer, immerses the most at once in the deionized water coagulating bath of 20 DEG C
20min, after film forming to be solidified, peels off film, continues to soak 24h in deionized water, the solvent that abjection is remaining, obtains shell and gathers
Sugar functional graphene oxide/Kynoar hybrid membranes.Wherein, by weight percentage, Kynoar and chitosan
The total amount of-graphene oxide is 17.7%, and chitosan-graphene oxide weight is the 0.2% of Kynoar weight, and porogen is
0.3%, organic solvent is 82%.Described porogen is Polyethylene Glycol；Described organic solvent is N-Methyl pyrrolidone；Described stream
Prolonging layer thickness is 130-180 μm.
Embodiment 4
1) preparation of chitosan-graphene oxide:
Chitosan is dissolved in the glacial acetic acid solution that volume fraction is 3%, is configured to the chitosan glacial acetic acid solution of mass fraction 1%；
Adding graphene oxide in deionized water, under room temperature, ultrasonic 1h, obtains graphene oxide dispersion；Under agitation by oxygen
Functionalized graphene dispersion liquid joins in chitosan glacial acetic acid solution, uses glacial acetic acid centrifuge washing for several times, move under room temperature after stirring 24h
Except unreacted chitosan, the most again with deionized water centrifuge washing the most for several times, vacuum drying, prepare chitosan-graphene oxide；
Wherein, graphene oxide is 1:10 with the mass ratio of chitosan；Gained chitosan-graphene oxide is laminar structured, and thickness is
2-3nm。
2) chitosan-graphene oxide is added in organic solvent, under room temperature after ultrasonic 1h, obtain chitosan-graphene oxide
Dispersion liquid；In chitosan-graphene oxide dispersion, add Kynoar and porogen, stir 30h at 50 DEG C, then at 50 DEG C
Lower standing and defoaming 20h, obtains casting solution, is then scraped equably on polyester non-woven fabric by casting solution, shape on polyester non-woven fabric
Become cast layer, immerse 15min in the deionized water coagulating bath of 30 DEG C the most at once, after film forming to be solidified, film is peeled off, continue
Soak 24h in deionized water, the solvent that abjection is remaining, obtain chitosan functional graphene oxide/Kynoar hydridization and surpass
Filter membrane.Wherein, by weight percentage, Kynoar is 17% with the total amount of chitosan-graphene oxide, chitosan-oxygen
Functionalized graphene weight is the 2% of Kynoar weight, and porogen is 5%, and organic solvent is 78%, chitosan-graphene oxide
Weight is the 0.2-2% of Kynoar weight.Described porogen is polyvinyl alcohol；Described organic solvent is dimethyl sulfoxide；Institute
Stating cast layer thickness is 130-180 μm.
Easily assemble in Kynoar membrane matrix to solve graphene oxide and make film hydrophilic, water flux and antipollution etc.
The problem that performance is restricted, first the present invention carries out covalent functionalization with chitosan to graphene oxide and is prepared for chitosan-oxidation
Graphene；Then, chitosan-graphene oxide ultrasonic disperse in organic solvent, Kynoar and porogen are added in one
Under fixed temperature, stirring and dissolving uniformly obtains casting solution, with water as coagulating bath, use immersion precipitation phase inversion process prepare chitosan-
Graphene oxide/Kynoar hybrid membranes.Chitosan-graphene oxide/polyvinylidene fluoride (PVDF) ultrafiltration membrane prepared by the present invention
Improve graphene oxide dispersibility in membrane matrix and at the aspects such as hydrophilic, water flux and antifouling property and oxidation stone
Ink alkene/polyvinylidene fluoride (PVDF) ultrafiltration membrane is compared, and has bigger lifting.
Claims (10)
1. chitosan functional graphene oxide/Kynoar hybrid membranes, it is characterised in that by weight percentage,
The raw material of ultrafilter membrane includes Kynoar 16-20%, porogen 0.3-5%, organic solvent 78-82% and chitosan-graphite oxide
Alkene；Wherein, chitosan-graphene oxide weight is the 0.2-2% of Kynoar weight.
A kind of chitosan functional graphene oxide/Kynoar hybrid membranes the most according to claim 1, its feature
It is, described Kynoar 110 DEG C of dry 10-15h in vacuum drying oven the most in advance.
A kind of chitosan functional graphene oxide/Kynoar hybrid membranes the most according to claim 1, its feature
Being, described porogen is the one in polyvinylpyrrolidone, Polyethylene Glycol, polyvinyl alcohol.
A kind of chitosan functional graphene oxide/Kynoar hybrid membranes the most according to claim 1, its feature
Being, described organic solvent is in dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide
Kind.
A kind of chitosan functional graphene oxide/Kynoar hybrid membranes the most according to claim 1, its feature
Being, described chitosan-graphene oxide is laminar structured, and thickness is 2-3nm.
6. the preparation method of chitosan functional graphene oxide/Kynoar hybrid membranes, it is characterised in that include
Following steps:
Chitosan-graphene oxide is added in organic solvent, ultrasonic under room temperature after, obtain chitosan-graphene oxide dispersion；
Adding Kynoar and porogen in chitosan-graphene oxide dispersion, stirring and dissolving is uniform, and standing and defoaming is cast
Film liquid, then scrapes on polyester non-woven fabric equably by casting solution, forms cast layer, immerse the most at once on polyester non-woven fabric
In coagulating bath, after film forming to be solidified, film is peeled off, continue to soak in deionized water, the solvent that abjection is remaining, obtain shell and gather
Sugar functional graphene oxide/Kynoar hybrid membranes；Wherein, by weight percentage, Kynoar is 16-20%,
Porogen is 0.3-5%, and organic solvent is 78-82%, and chitosan-graphene oxide weight is the 0.2-2% of Kynoar weight.
The preparation side of a kind of chitosan functional graphene oxide/Kynoar hybrid membranes the most according to claim 6
Method, it is characterised in that described chitosan-graphene oxide prepares by the following method:
Chitosan is dissolved in the glacial acetic acid solution that volume fraction is 1-3%, is configured to the chitosan glacial acetic acid of mass fraction 1-3%
Solution；
Adding graphene oxide in deionized water, under room temperature, ultrasonic 1h, obtains graphene oxide dispersion；Under agitation by oxygen
Functionalized graphene dispersion liquid joins in chitosan glacial acetic acid solution, uses glacial acetic acid centrifuge washing for several times, move under room temperature after stirring 24h
Except unreacted chitosan, the most again with deionized water centrifuge washing the most for several times, vacuum drying, prepare chitosan-graphene oxide；
Wherein, graphene oxide is 1:10 with the mass ratio of chitosan；Gained chitosan-graphene oxide is laminar structured, and thickness is
2-3nm。
The preparation side of a kind of chitosan functional graphene oxide/Kynoar hybrid membranes the most according to claim 6
Method, it is characterised in that described ultrasonic time is 1h, the temperature of stirring is 40-60 DEG C, and the time of stirring is 24-36h；Described
The temperature of standing and defoaming be 40-60 DEG C, the time of standing and defoaming is 12-24h.
The preparation side of a kind of chitosan functional graphene oxide/Kynoar hybrid membranes the most according to claim 6
Method, it is characterised in that described coagulating bath is deionized water, water temperature is 20-30 DEG C；Time in described immersion coagulating bath is
15-20min；Described porogen is the one in polyvinylpyrrolidone, Polyethylene Glycol, polyvinyl alcohol；Described organic solvent is
One in dimethylformamide, dimethyl acetylamide, N-Methyl pyrrolidone, dimethyl sulfoxide.
The preparation of a kind of chitosan functional graphene oxide/Kynoar hybrid membranes the most according to claim 6
Method, it is characterised in that described cast layer thickness is 130-180 μm；The described immersion time in deionized water is 24-48h.
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| CN113457472A (en) * | 2021-03-15 | 2021-10-01 | 波塞冬(江苏)新材料科技有限公司 | Graphene modified PVDF high-performance composite membrane and preparation method thereof |
| CN113318611A (en) * | 2021-05-31 | 2021-08-31 | 天津工业大学 | Hollow fiber ultrafiltration membrane with lasting high pollution resistance and preparation method thereof |
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| CN115155328B (en) * | 2022-07-08 | 2024-04-19 | 安庆市鑫祥瑞环保科技有限公司 | Polymer ultrafiltration membrane for sewage treatment and preparation method thereof |
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