CN108479424A - Preparation method of modified polyvinylidene fluoride membrane - Google Patents
Preparation method of modified polyvinylidene fluoride membrane Download PDFInfo
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- CN108479424A CN108479424A CN201810282720.XA CN201810282720A CN108479424A CN 108479424 A CN108479424 A CN 108479424A CN 201810282720 A CN201810282720 A CN 201810282720A CN 108479424 A CN108479424 A CN 108479424A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229920002981 polyvinylidene fluoride Polymers 0.000 title abstract description 29
- 239000002033 PVDF binder Substances 0.000 title abstract description 28
- 239000012528 membrane Substances 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 103
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 102
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000463 material Substances 0.000 claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 18
- 239000011941 photocatalyst Substances 0.000 claims abstract description 18
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 13
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 12
- 238000005266 casting Methods 0.000 claims abstract description 11
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 235000019441 ethanol Nutrition 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 6
- 239000010439 graphite Substances 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 34
- 238000002604 ultrasonography Methods 0.000 claims description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 20
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 2
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 4
- 239000007864 aqueous solution Substances 0.000 abstract 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 abstract 1
- 238000001704 evaporation Methods 0.000 abstract 1
- 238000007790 scraping Methods 0.000 abstract 1
- 239000010865 sewage Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 9
- 239000004408 titanium dioxide Substances 0.000 description 9
- 230000003373 anti-fouling effect Effects 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 230000001934 delay Effects 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 238000009285 membrane fouling Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Classifications
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention discloses a preparation method of a modified polyvinylidene fluoride membrane, which comprises the following steps: firstly, preparing graphite into graphene oxide; dissolving graphene oxide and polyethylene glycol in an ethanol aqueous solution, stirring and heating to obtain a material B; adding butyl titanate and sulfuric acid into absolute ethyl alcohol, stirring, mixing with the material B, and mixing with a dimethylformamide aqueous solution to obtain a composite photocatalyst; mixing a composite photocatalyst with dimethylacetamide, carrying out ultrasonic treatment, adding a pore-forming agent, continuing ultrasonic treatment, adding polyvinylidene fluoride, standing and defoaming to obtain a membrane casting solution, scraping a membrane, pre-evaporating, immersing in deionized water, and standing to obtain a modified polyvinylidene fluoride membrane. The modified polyvinylidene fluoride membrane prepared by the preparation method provided by the invention has the advantages of excellent anti-pollution performance, obvious degradation effect on organic matters in sewage, long service life and the like.
Description
Technical field
The present invention relates to filtering technical field of membrane more particularly to a kind of preparation methods of modified polyvinilidene fluoride film.
Background technology
In recent years, development of the membrane technology in chemical wastewater treatment field causes very extensive interest.Kynoar
(PVDF) film is commonly used for chemical wastewater treatment field, but poly- with the advantage that nontoxic, chemical property is stable, resistance to pH range is wide
Vinylidene fluoride film hydrophobicity is strong, and in the separation for aqueous based systems, fouling membrane is serious, while to the degradation of dirty Organic substance in water
Performance is general, limits the use of polyvinylidene fluoride film.
Invention content
Technical problems based on background technology, the present invention propose a kind of preparation side of modified polyvinilidene fluoride film
Method, obtained modified polyvinilidene fluoride film has antifouling property excellent, apparent to the degradation effect of dirty Organic substance in water, uses
The advantages that long lifespan.
A kind of preparation method of modified polyvinilidene fluoride film proposed by the present invention, includes the following steps：
S1, material A is prepared using Hummers methods are improved in graphite, then is removed by ultrasound, freeze-drying obtains
Graphene oxide；
S2, graphene oxide and polyethylene glycol are dissolved in ethanol water, agitating and heating, obtain material B；
S3, butyl titanate and sulfuric acid being added in absolute ethyl alcohol, then stirring is mixed with material B, cooling, is centrifuged,
Washing, then mixes with dimethylformamide in water, hydro-thermal reaction, centrifuges, and washing obtains composite photo-catalyst；
S4, agent is urged to be mixed with dimethylacetylamide complex light, then pore-foaming agent is added in ultrasound, continue ultrasound, add
Kynoar, standing and defoaming obtain casting solution, then knifing, prevapourising, then immerse in deionized water, stand, are modified
Polyvinylidene fluoride film.
Preferably, in S1, by weight by 2-3 parts of natural flake graphites and 15-18 parts of KMnO4The concentrated sulfuric acid is added in mixing
And concentrated phosphoric acid is subsequently poured into 45-55 DEG C of stirred in water bath 11-13h in 300-400 parts of ice, stands 12-14h, centrifugation point
From being washed with distilled water to neutrality, freeze 3.5-4.5h, re-dry 22-26h, obtain material A, then pass through ultrasound stripping, freezing
It is dry, obtain graphene oxide.
Preferably, the volume ratio between the concentrated sulfuric acid and concentrated phosphoric acid is 9-18:1-2.
Preferably, also containing the hydrogen peroxide that 2-3 parts of volumetric concentrations are 25-35% in ice.
Preferably, in S2,2-5 parts of graphene oxides and 3-5 parts of polyethylene glycol are dissolved in ethanol water by weight
In, it is heated with stirring to 70-90 DEG C, obtains material B.
Preferably, in S2, the volume ratio of second alcohol and water is 50-70 in ethanol water:8-12.
Preferably, in S3, butyl titanate and sulfuric acid are added in absolute ethyl alcohol, then stirring is mixed with material B, in 70-
8-15h is stirred under 90 DEG C of temperature conditions, it is cooling, it centrifuges, is washed with water, is then mixed with dimethylformamide in water,
The hydro-thermal reaction in the stainless steel autoclave of polytetrafluoroethyllining lining, is centrifuged, and is washed with water, and obtains composite photocatalyst
Agent.
Preferably, the volume ratio between butyl titanate, sulfuric acid, absolute ethyl alcohol, dimethylformamide in water, material B is
15-20:6.5-7.5:500-1000:2500-2600:2.5-3.5；Wherein, dimethyl formyl in dimethylformamide in water
Volume ratio between amine and water is 25:0.2-0.8.
Preferably, in hydrothermal reaction process, reaction temperature is 180-220 DEG C, reaction time 18-22h.
Preferably, in S4, agent is urged to be mixed with 80-84 parts of dimethylacetylamides 0.15-0.2 parts of complex lights by weight,
Ultrasonic 25-35min is then slowly added into 1-3 parts of polyvinylpyrrolidones, continues ultrasound 8-12min, adds 15-20 parts and gathers
Vinylidene stands deaeration after 20-30h, obtains casting solution, then knifing in 45-55 DEG C of stirred in water bath 22-26h, pre- to steam
1-2min is sent out, then is immersed in deionized water, stands, obtains modified polyvinilidene fluoride film.
By graphene oxide and polyethylene glycol blending in the present invention, and complex is carried out by hydro-thermal reaction and titanium dioxide
At composite photo-catalyst, wherein by introducing graphene oxide, the photocatalytic activity of titanium dioxide is effectively improved, then by this
Composite photo-catalyst is blended with Kynoar (PVDF), is effectively improved the hydrophily and permeability of Kynoar, is obtained
The modified polyvinilidene fluoride film contact angle arrived reduces amplitude maximum, and hydrophilicity is excellent.Again by modified polyvinilidene fluoride film
Antifouling property is tested after ultraviolet light, through ultraviolet light post-modification polyvinylidene fluoride film (i.e. TiO2-GO-
PEG-PVDF films) compared to TiO2-PVDF films and GO-PVDF films (i.e. graphene oxide-polyvinylidene fluoride film), resistance tocrocking
It can be remarkably reinforced.The present invention proposes a kind of preparation method of modified polyvinilidene fluoride film, by optimizing preparation process, obtains
Modified polyvinilidene fluoride film has antifouling property excellent, apparent to the degradation effect of dirty Organic substance in water, service life length etc.
Advantage.
Description of the drawings
Fig. 1 is composite photo-catalyst and graphene oxide, the photocatalytic degradation curve of titanium dioxide in the embodiment of the present invention 1
Figure；
Fig. 2 is modified polyvinilidene fluoride film electron microscope in the embodiment of the present invention 1；
Fig. 3 is for TiO2-GO-PEG-PVDF films in the embodiment of the present invention 1 with TiO2-PVDF films, GO-PVDF films in ultraviolet light
Antifouling property figure after irradiation.
Specific implementation mode
In the following, technical scheme of the present invention is described in detail by specific embodiment.
Embodiment 1
A kind of preparation method of modified polyvinilidene fluoride film proposed by the present invention, includes the following steps：
S1, material A is prepared using Hummers methods are improved in graphite, then is removed by ultrasound, freeze-drying obtains
Graphene oxide；
S2,3.5 parts of graphene oxides and 2.5 parts of polyethylene glycol are dissolved in ethanol water by weight, stirring plus
Heat obtains material B to 80 DEG C；Wherein, the volume ratio of second alcohol and water is 70 in ethanol water:10；
S3, butyl titanate and sulfuric acid are added in absolute ethyl alcohol, then stirring is mixed with material B, in 80 DEG C of temperature conditions
Lower stirring 12h, it is cooling, it centrifuges, is washed with water, is then mixed with dimethylformamide in water, in polytetrafluoroethylene (PTFE)
Hydro-thermal reaction in the stainless steel autoclave of lining, is centrifuged, and is washed with water, and obtains composite photo-catalyst；Wherein, metatitanic acid fourth
Volume ratio between ester, sulfuric acid, absolute ethyl alcohol, dimethylformamide in water, material B is 15:7:700:2550:3；Wherein,
Volume ratio in dimethylformamide in water between dimethylformamide and water is 25:0.5；In hydrothermal reaction process, reaction
Temperature is 200 DEG C, reaction time 20h；
S4, agent is urged to be mixed with 84 parts of dimethylacetylamides 0.15 part of complex light by weight, then ultrasonic 30min delays
Slowly 1 part of polyvinylpyrrolidone is added, continues ultrasound 10min, 15 parts of Kynoar is added, in 50 DEG C of stirred in water bath
For 24 hours, deaeration after standing 26h, obtains casting solution, then knifing, prevapourising 1.5min, then immerses in deionized water, stands, obtains
Modified polyvinilidene fluoride film (i.e. TiO2-GO-PEG-PVDF films).
Embodiment 2
A kind of preparation method of modified polyvinilidene fluoride film proposed by the present invention, includes the following steps：
S1, material A is prepared using Hummers methods are improved in graphite, then is removed by ultrasound, freeze-drying obtains
Graphene oxide；
S2,2.5 parts of graphene oxides and 3 parts of polyethylene glycol are dissolved in ethanol water by weight, agitating and heating
To 80 DEG C, material B is obtained；Wherein, the volume ratio of second alcohol and water is 65 in ethanol water:12；
S3, butyl titanate and sulfuric acid are added in absolute ethyl alcohol, then stirring is mixed with material B, in 80 DEG C of temperature conditions
Lower stirring 12h, it is cooling, it centrifuges, is washed with water, is then mixed with dimethylformamide in water, in polytetrafluoroethylene (PTFE)
Hydro-thermal reaction in the stainless steel autoclave of lining, is centrifuged, and is washed with water, and obtains composite photo-catalyst；Wherein, metatitanic acid fourth
Volume ratio between ester, sulfuric acid, absolute ethyl alcohol, dimethylformamide in water, material B is 18:7.5:500:2500:2.5；Its
In, the volume ratio in dimethylformamide in water between dimethylformamide and water is 25:0.5；In hydrothermal reaction process, instead
It is 200 DEG C to answer temperature, reaction time 20h；
S4, agent is urged to be mixed with 80 parts of dimethylacetylamides 0.18 part of complex light by weight, then ultrasonic 30min delays
Slowly 1.2 parts of polyvinylpyrrolidones are added, continues ultrasound 10min, 15 parts of Kynoar is added, in 45 DEG C of stirred in water bath
26h stands deaeration after 20h, obtains casting solution, then knifing, prevapourising 1min, then immerses in deionized water, stands, is changed
Property polyvinylidene fluoride film.
Embodiment 3
A kind of preparation method of modified polyvinilidene fluoride film proposed by the present invention, includes the following steps：
S1, material A is prepared using Hummers methods are improved in graphite, then is removed by ultrasound, freeze-drying obtains
Graphene oxide；
S2,4.5 parts of graphene oxides and 4 parts of polyethylene glycol are dissolved in ethanol water by weight, agitating and heating
To 80 DEG C, material B is obtained；Wherein, the volume ratio of second alcohol and water is 60 in ethanol water:8；
S3, butyl titanate and sulfuric acid are added in absolute ethyl alcohol, then stirring is mixed with material B, in 80 DEG C of temperature conditions
Lower stirring 12h, it is cooling, it centrifuges, is washed with water, is then mixed with dimethylformamide in water, in polytetrafluoroethylene (PTFE)
Hydro-thermal reaction in the stainless steel autoclave of lining, is centrifuged, and is washed with water, and obtains composite photo-catalyst；Wherein, metatitanic acid fourth
Volume ratio between ester, sulfuric acid, absolute ethyl alcohol, dimethylformamide in water, material B is 20:6.5:800:2600:3.5；Its
In, the volume ratio in dimethylformamide in water between dimethylformamide and water is 25:0.5；In hydrothermal reaction process, instead
It is 200 DEG C to answer temperature, reaction time 20h；
S4, agent is urged to be mixed with 80 parts of dimethylacetylamides 0.19 part of complex light by weight, then ultrasonic 30min delays
Slowly 1 part of polyvinylpyrrolidone is added, continues ultrasound 10min, 15 parts of Kynoar is added, in 50 DEG C of stirred in water bath
25h stands deaeration after 25h, obtains casting solution, then knifing, prevapourising 2min, then immerses in deionized water, stands, is changed
Property polyvinylidene fluoride film.
Embodiment 4
A kind of preparation method of modified polyvinilidene fluoride film proposed by the present invention, includes the following steps：
S1, by weight by 2 parts of natural flake graphites and 15 parts of KMnO4The concentrated sulfuric acid and concentrated phosphoric acid is added, at 45 DEG C in mixing
Stirred in water bath 13h, be subsequently poured into 300 parts of ice, stand 12h, centrifuge, be washed with distilled water to neutrality, freeze
3.5h, re-dry 22h obtain material A, then are removed by ultrasound, and freeze-drying obtains graphene oxide；Wherein, the concentrated sulfuric acid and
Volume ratio between concentrated phosphoric acid is 9:1；The hydrogen peroxide for being also 35% containing 2 parts of volumetric concentrations in ice；
S2,2 parts of graphene oxides and 3 parts of polyethylene glycol are dissolved in ethanol water by weight, are heated with stirring to
70 DEG C, obtain material B；Wherein, the volume ratio of second alcohol and water is 50 in ethanol water:8；
S3, butyl titanate and sulfuric acid are added in absolute ethyl alcohol, then stirring is mixed with material B, in 70 DEG C of temperature conditions
Lower stirring 15h, it is cooling, it centrifuges, is washed with water, is then mixed with dimethylformamide in water, in polytetrafluoroethylene (PTFE)
Hydro-thermal reaction in the stainless steel autoclave of lining, is centrifuged, and is washed with water, and obtains composite photo-catalyst；Wherein, metatitanic acid fourth
Volume ratio between ester, sulfuric acid, absolute ethyl alcohol, dimethylformamide in water, material B is 15:6.5:500:2600:3；Its
In, the volume ratio in dimethylformamide in water between dimethylformamide and water is 25:0.2；In hydrothermal reaction process, instead
It is 180 DEG C to answer temperature, reaction time 22h；
S4, agent is urged to be mixed with 84 parts of dimethylacetylamides 0.2 part of complex light by weight, ultrasonic 35min, then slowly
3 parts of polyvinylpyrrolidones are added, continues ultrasound 12min, adds 20 parts of Kynoar, in 55 DEG C of stirred in water bath 22h,
Deaeration after standing 30h, obtains casting solution, then knifing, prevapourising 1min, then immerses in deionized water, stands, and obtains modified poly-
Vinylidene fluoride film.
Embodiment 5
A kind of preparation method of modified polyvinilidene fluoride film proposed by the present invention, includes the following steps：
S1, by weight by 3 parts of natural flake graphites and 18 parts of KMnO4The concentrated sulfuric acid and concentrated phosphoric acid is added, at 55 DEG C in mixing
Stirred in water bath 11h, be subsequently poured into 400 parts of ice, stand 14h, centrifuge, be washed with distilled water to neutrality, freeze
4.5h, re-dry 26h obtain material A, then are removed by ultrasound, and freeze-drying obtains graphene oxide；Wherein, the concentrated sulfuric acid and
Volume ratio between concentrated phosphoric acid is 15:1；The hydrogen peroxide for being also 25% containing 3 parts of volumetric concentrations in ice；
S2,5 parts of graphene oxides and 5 parts of polyethylene glycol are dissolved in ethanol water by weight, are heated with stirring to
90 DEG C, obtain material B；Wherein, the volume ratio of second alcohol and water is 70 in ethanol water:12；
S3, butyl titanate and sulfuric acid are added in absolute ethyl alcohol, then stirring is mixed with material B, in 90 DEG C of temperature conditions
Lower stirring 8h, it is cooling, it centrifuges, is washed with water, is then mixed with dimethylformamide in water, in polytetrafluoroethyllining lining
Stainless steel autoclave in hydro-thermal reaction, be centrifuged, be washed with water, obtain composite photo-catalyst；Wherein, butyl titanate,
Volume ratio between sulfuric acid, absolute ethyl alcohol, dimethylformamide in water, material B is 20:7.5:1000:2500:2.5；Its
In, the volume ratio in dimethylformamide in water between dimethylformamide and water is 25:0.8；In hydrothermal reaction process, instead
It is 220 DEG C to answer temperature, reaction time 18h；
S4, agent is urged to be mixed with 80 parts of dimethylacetylamides 0.15 part of complex light by weight, then ultrasonic 25min delays
Slowly 1 part of polyvinylpyrrolidone is added, continues ultrasound 8min, 15 parts of Kynoar is added, in 45 DEG C of stirred in water bath
26h stands deaeration after 20h, obtains casting solution, then knifing, prevapourising 2min, then immerses in deionized water, stands, is changed
Property polyvinylidene fluoride film.
Embodiment 6
A kind of preparation method of modified polyvinilidene fluoride film proposed by the present invention, includes the following steps：
S1, by weight by 2.5 parts of natural flake graphites and 16.5 parts of KMnO4The concentrated sulfuric acid and concentrated phosphoric acid is added in mixing,
48 DEG C of stirred in water bath 12h is subsequently poured into 360 parts of ice, stands 13h, is centrifuged, is washed with distilled water to neutrality, cold
Freeze 4h, re-dry for 24 hours, obtains material A, then remove by ultrasound, freeze-drying obtains graphene oxide；Wherein, the concentrated sulfuric acid and
Volume ratio between concentrated phosphoric acid is 10:1；The hydrogen peroxide for being also 30% containing 2.5 parts of volumetric concentrations in ice；
S2,4 parts of graphene oxides and 4 parts of polyethylene glycol are dissolved in ethanol water by weight, are heated with stirring to
82 DEG C, obtain material B；Wherein, the volume ratio of second alcohol and water is 60 in ethanol water:10；
S3, butyl titanate and sulfuric acid are added in absolute ethyl alcohol, then stirring is mixed with material B, in 82 DEG C of temperature conditions
Lower stirring 12h, it is cooling, it centrifuges, is washed with water, is then mixed with dimethylformamide in water, in polytetrafluoroethylene (PTFE)
Hydro-thermal reaction in the stainless steel autoclave of lining, is centrifuged, and is washed with water, and obtains composite photo-catalyst；Wherein, metatitanic acid fourth
Volume ratio between ester, sulfuric acid, absolute ethyl alcohol, dimethylformamide in water, material B is 17.5:7.5:800:2560:3.2；
Wherein, the volume ratio in dimethylformamide in water between dimethylformamide and water is 25:0.6；In hydrothermal reaction process,
Reaction temperature is 210 DEG C, reaction time 19h；
S4, agent is urged to be mixed with 82 parts of dimethylacetylamides 0.16 part of complex light by weight, then ultrasonic 32min delays
Slowly 1.5 parts of polyvinylpyrrolidones are added, continues ultrasound 9min, 18 parts of Kynoar is added, in 52 DEG C of stirred in water bath
23h stands deaeration after 22h, obtains casting solution, then knifing, prevapourising 2min, then immerses in deionized water, stands, is changed
Property polyvinylidene fluoride film.
Performance detection is carried out to the modified polyvinilidene fluoride film that is prepared in the embodiment of the present invention 1, obtain Fig. 1, Fig. 2 and
Fig. 3.
Wherein, Fig. 1 is that the photocatalysis of composite photo-catalyst and graphene oxide, titanium dioxide in the embodiment of the present invention 1 is dropped
Solution curve figure, i.e. composite photo-catalyst and graphene oxide, titanium dioxide and the degradation property design sketch to dirty Organic substance in water.
The catalytic efficiency of different catalysts has very big difference as seen from Figure 1.The contrast experiment of titanium dioxide illustrate titanium dioxide as
Semi-conducting material has certain photocatalytic activity, but since titanium dioxide excites the electron-hole of generation under ultraviolet light
Compound equal self shortcomings are easy to, only titanium dioxide is caused to have certain limitation as catalysis material progress light degradation experiment
Property, photocatalytic activity is relatively low.And another contrast experiment's selective oxidation graphene aoxidizes stone as seen from the figure as photochemical catalyst
For black alkene under ultraviolet light almost without any photocatalytic activity, degradation efficiency is extremely low.Lower titanium dioxide-the graphene oxide of comparison
Composite photo-catalyst but shows that stronger photocatalysis performance, photocatalytic degradation efficiency significantly improve, to dirty Organic substance in water
Good degrading effect.
Fig. 2 is the electron microscope of modified polyvinilidene fluoride film Modified Membrane in the embodiment of the present invention 1, utilizes TiO2- as shown in Figure 2
The pore size distribution size distribution for the modified polyvinilidene fluoride film that GO-PEG modified polyvinilidene fluorides obtain is uniform, has good hydrophilic
And permeance property.
Fig. 3 is for TiO2-GO-PEG-PVDF films in the embodiment of the present invention 1 with TiO2-PVDF films, GO-PVDF films in ultraviolet light
Antifouling property figure after irradiation, wherein Rt is gross contamination rate, and Rr is reversible membrane fouling, and Rir is irreversible membrane fouling；As shown in Figure 3
Under conditions of reversible membrane fouling is almost the same, the irreversible membrane fouling ratio TiO2-PVDF films and GO- of TiO2-GO-PEG-PVDF films
Pvdf membrane is small, illustrates the antifouling property ratio TiO2 Modified Membranes and GO Modified Membranes of TiO2-GO Modified Membranes under identical condition
It is excellent.
By Fig. 1, Fig. 2 and Fig. 3 it is found that modified polyvinilidene fluoride film antifouling property proposed by the present invention is excellent, to dirt
The degradation effect of Organic substance in water is apparent, is suitable for producing and using.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of modified polyvinilidene fluoride film, which is characterized in that include the following steps：
S1, material A is prepared using Hummers methods are improved in graphite, then is removed by ultrasound, freeze-drying is aoxidized
Graphene；
S2, graphene oxide and polyethylene glycol are dissolved in ethanol water, agitating and heating, obtain material B；
S3, butyl titanate and sulfuric acid are added in absolute ethyl alcohol, then stirring is mixed with material B, cooling, is centrifuged, is washed
It washs, is then mixed with dimethylformamide in water, hydro-thermal reaction centrifuges, and washing obtains composite photo-catalyst；
S4, agent is urged to be mixed with dimethylacetylamide complex light, then pore-foaming agent is added in ultrasound, continue ultrasound, adds poly- inclined
Vinyl fluoride, standing and defoaming obtain casting solution, then knifing, prevapourising, then immerse in deionized water, stand, obtain modified polyvinilidene
Fluoride film.
2. the preparation method of modified polyvinilidene fluoride film according to claim 1, which is characterized in that in S1, by weight will
2-3 parts of natural flake graphites and 15-18 parts of KMnO4The concentrated sulfuric acid and concentrated phosphoric acid is added, in 45-55 DEG C of stirred in water bath in mixing
11-13h is subsequently poured into 300-400 parts of ice, stands 12-14h, is centrifuged, and neutrality is washed with distilled water to, and freezes 3.5-
4.5h, re-dry 22-26h obtain material A, then are removed by ultrasound, and freeze-drying obtains graphene oxide.
3. the preparation method of modified polyvinilidene fluoride film according to claim 1, which is characterized in that the concentrated sulfuric acid and concentrated phosphoric acid it
Between volume ratio be 9-18:1-2.
4. the preparation method of modified polyvinilidene fluoride film according to claim 1, which is characterized in that also contain 2-3 parts in ice
Volumetric concentration is the hydrogen peroxide of 25-35%.
5. the preparation method of modified polyvinilidene fluoride film according to claim 1, which is characterized in that in S2, by weight will
2-5 parts of graphene oxides and 3-5 parts of polyethylene glycol are dissolved in ethanol water, are heated with stirring to 70-90 DEG C, are obtained material B.
6. the preparation method of modified polyvinilidene fluoride film according to claim 5, which is characterized in that in S2, ethanol water
The volume ratio of middle second alcohol and water is 50-70:8-12.
7. the preparation method of modified polyvinilidene fluoride film according to claim 1, which is characterized in that in S3, by butyl titanate
It being added in absolute ethyl alcohol with sulfuric acid, then stirring mixes with material B, 8-15h is stirred under 70-90 DEG C of temperature condition, cooling,
It centrifuges, is washed with water, is then mixed with dimethylformamide in water, in the stainless steel autoclave of polytetrafluoroethyllining lining
Middle hydro-thermal reaction, is centrifuged, and is washed with water, and obtains composite photo-catalyst.
8. the preparation method of modified polyvinilidene fluoride film according to claim 7, which is characterized in that butyl titanate, sulfuric acid, nothing
Volume ratio between water-ethanol, dimethylformamide in water, material B is 15-20:6.5-7.5:500-1000:2500-
2600:2.5-3.5；Wherein, the volume ratio in dimethylformamide in water between dimethylformamide and water is 25:0.2-
0.8。
9. the preparation method of modified polyvinilidene fluoride film according to claim 7, which is characterized in that in hydrothermal reaction process,
Reaction temperature is 180-220 DEG C, reaction time 18-22h.
10. the preparation method of modified polyvinilidene fluoride film according to claim 1, which is characterized in that in S4, by weight will
0.15-0.2 parts of complex lights urge agent to be mixed with 80-84 parts of dimethylacetylamides, and ultrasonic 25-35min is then slowly added into 1-3 parts
Polyvinylpyrrolidone continues ultrasound 8-12min, 15-20 parts of Kynoar is added, in 45-55 DEG C of stirred in water bath 22-
26h stands deaeration after 20-30h, obtains casting solution, then knifing, prevapourising 1-2min, then immerses in deionized water, stands,
Obtain modified polyvinilidene fluoride film.
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| CN109277005A (en) * | 2018-09-30 | 2019-01-29 | 天津市金鳞水处理科技有限公司 | A kind of polyvinylidene fluoride modified composite membrane |
| CN109277006A (en) * | 2018-09-30 | 2019-01-29 | 天津市金鳞水处理科技有限公司 | A kind of preparation method of polyvinylidene fluoride modified composite membrane |
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