CN106215717B - A kind of preparation method of compound PVDF ultrafiltration membrane - Google Patents
A kind of preparation method of compound PVDF ultrafiltration membrane Download PDFInfo
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- CN106215717B CN106215717B CN201610640836.7A CN201610640836A CN106215717B CN 106215717 B CN106215717 B CN 106215717B CN 201610640836 A CN201610640836 A CN 201610640836A CN 106215717 B CN106215717 B CN 106215717B
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- 239000012528 membrane Substances 0.000 title claims abstract description 100
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 19
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 title claims abstract description 16
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 74
- 229960003638 dopamine Drugs 0.000 claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 claims abstract description 29
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 25
- 125000003118 aryl group Chemical group 0.000 claims abstract description 24
- -1 amido modified titania Chemical class 0.000 claims abstract description 18
- 238000004140 cleaning Methods 0.000 claims abstract description 11
- 229920001690 polydopamine Polymers 0.000 claims abstract description 11
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 10
- 239000007853 buffer solution Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 125000003368 amide group Chemical group 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- SNRUBQQJIBEYMU-NJFSPNSNSA-N dodecane Chemical compound CCCCCCCCCCC[14CH3] SNRUBQQJIBEYMU-NJFSPNSNSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 2
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 claims 2
- 229960004502 levodopa Drugs 0.000 claims 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical group CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims 1
- 125000001340 2-chloroethyl group Chemical class [H]C([H])(Cl)C([H])([H])* 0.000 claims 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims 1
- 238000007598 dipping method Methods 0.000 claims 1
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical class ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 claims 1
- 239000003205 fragrance Substances 0.000 claims 1
- 239000008187 granular material Substances 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 13
- 230000003373 anti-fouling effect Effects 0.000 abstract description 7
- 239000003344 environmental pollutant Substances 0.000 abstract description 7
- 231100000719 pollutant Toxicity 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 230000005855 radiation Effects 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- FNYLWPVRPXGIIP-UHFFFAOYSA-N Triamterene Chemical compound NC1=NC2=NC(N)=NC(N)=C2N=C1C1=CC=CC=C1 FNYLWPVRPXGIIP-UHFFFAOYSA-N 0.000 description 16
- 230000004907 flux Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 235000010215 titanium dioxide Nutrition 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 229920001059 synthetic polymer Polymers 0.000 description 6
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 4
- 230000010148 water-pollination Effects 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 239000012460 protein solution Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-UHFFFAOYSA-N 0.000 description 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical class NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- RPAUSEIPGITIDG-UHFFFAOYSA-N C1=CC=CC=C1.C(C)O[SiH](OCC)OCC Chemical compound C1=CC=CC=C1.C(C)O[SiH](OCC)OCC RPAUSEIPGITIDG-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 229960000281 trometamol Drugs 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/12—Composite membranes; Ultra-thin membranes
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Catalysts (AREA)
Abstract
The invention discloses the preparation methods of a kind of preparation method of separation membrane, in particular to a kind of antipollution and the compound PVDF ultrafiltration membrane of light clean type.The present invention is by coating dopamine, from the pvdf membrane of poly-dopamine is grafted aromatic polycarboxylic acyl chlorides, amido modified titania nanoparticles are grafted on pvdf membrane and antipollution and the compound PVDF ultrafiltration membrane of light clean type is prepared on pvdf membrane surface.It is an advantage of the invention that the autohemagglutination by dopamine on pvdf membrane surface forms a poly-dopamine coat, because hydroxyl and amino isoreactivity group that dopamine has, improve the antifouling property of pvdf membrane；When pollutant adsorbs or deposits, for nano-titanium dioxide under ultraviolet radiation, pollutant reaches the self-cleaning purpose of film light by catalytic degradation.
Description
Technical field
The invention patent relates to separation membrane technical field, in particular to a kind of antipollutions and the compound PVDF of light clean type
The preparation method of ultrafiltration membrane.
Background technique
Membrane separation technique is a kind of efficient, energy-efficient green new separation technology, simple, the operating condition temperature with equipment
With the outstanding features such as treating capacity is big, separative efficiency is high, in seawater and brackish water desalination, wastewater treatment and recycling, biology system
The fields such as product separation, environmental project, drink water purifying, air filtration and purification, material concentration and separation are used widely, and
Achieve good economic and social benefit.
Polymeric membrane for separation can be divided into microfiltration membranes, ultrafiltration membrane, nanofiltration membrane and reverse osmosis membrane according to its pore size.According to
High molecular material source is different, can be divided by the polymeric membrane for separation of natural macromolecular material preparation and by synthetic polymer system
Standby polymeric membrane for separation.Natural macromolecular material is mainly cellulose acetate and its derivative, and synthetic polymer then kind
It is relatively more, it mainly include polysulfones synthetic polymer, polyamide-based synthetic polymer, polyesters synthetic polymer, polyolefin
Class synthetic polymer etc..Polymeric membrane for separation can be divided into dissymmetrical structure seperation film, symmetrical structure point according to structure difference
From film and separation membrane with composite structure；Plate high-molecular porous film, hollow fiber polymer perforated membrane and pipe can be divided into according to shape
Shape high-molecular porous film.Different high-molecular porous films has different purposes according to differences such as its aperture, materials.
Hyperfiltration technique is a kind of purification for being widely used in water, and solution separation is concentrated, and recovers useful materials from waste water
The new and high technology in field.Using hyperfiltration technique during handling water, the stability of film is an important parameter.Due to useless
Often there is protein pollutant in water, after filtering for a long time, pollutant can be adsorbed on the surface of film, so as to cause the flux of film
It reduces, influences the performance of film；And remove these film surface pollutants and generally require periodically to be backwashed, such as physical cleaning or
Person's chemical cleaning reduces production efficiency to increase operating cost.
As one of ultrafiltration membrane material Kynoar (referred to as PVDF) because its excellent heat resistance, mechanical performance,
Radiation resistance, chemical stability etc. have great potentiality in seperation film application field.However the surface of PVDF can be very low, profit
Wet performance is poor, and strong-hydrophobicity greatly reduces pure water flux.Hydrophobic pvdf membrane is easy to be contained natural organic substance (such as
Protein) solution to be processed polluted, the substances such as protein are easily adsorbed on film surface or blocking fenestra, cause infiltration logical.
Have a large amount of paper and patent report at present, by TiO2Nano particle is blended to form casting solution preparation with PVDF powder
Inorganic-organic hybrid pvdf membrane, can be improved the hydrophily of film, to improve its resistance tocrocking.But when due to being blended, TiO2
Particle is embedded by pvdf membrane matrix mostly, improves limitation for hydrophily, and also will cause a degree of film defect,
So as to cause film properties decline.Also there is research worker in order to solve this problem, using the method for self assembly, by TiO2Nanometer
It is particle coated to overcome problem above in film surface.By this method processing after, the hydrophily and resistance tocrocking of film have compared with
It is big to improve, but this method is only applicable to inherently more hydrophilic membrane material, because only that just can guarantee TiO in this way2With base
The active force of body film, to guarantee TiO2Can be stable be covered on film surface, therefore, the method can not be widely applied.
Film surface grafting modification is one kind under conditions of not changing membrane body structure, by the object with certain specific function
Matter is grafted to film surface by covalent bond, causes the separation of film and antifouling property more significant.The present invention is that will have light to urge
The titanium dioxide nanoparticle for changing function and good hydrophilic property, by dopamine and pyromellitic trimethylsilyl chloride as graft, by amino
The titanium dioxide nanoparticle of modification is successfully grafted on pvdf membrane, so that the pvdf membrane of commodity has good antipollution and light
Cleaning function.
Summary of the invention
The present invention be directed to pvdf membrane surfaces can be low, and hydrophobicity is strong, and resistance tocrocking is poor, cannot achieve showing for light cleaning function
Shape proposes a kind of the nano-titanium dioxide with photo-catalysis function and good hydrophilic property to be grafted to pvdf membrane table by crosslinking technology
Pvdf membrane antipollution and light cleaning function are realized in face.
The technical solution for realizing the aim of the invention is as follows: a kind of system of antipollution and the compound PVDF ultrafiltration membrane of light clean type
Preparation Method, comprising the following steps:
Step 1, cleaning commodity pvdf membrane: the pvdf membrane of commodity is immersed in dehydrated alcohol for 24 hours, deionized water is then used
It cleans repeatedly；
Step 2 prepares dopamine solution: dopamine is dissolved into the Tris-HCI buffer solution that pH value is 8.5；Tris-
The Chinese nickname of HCI buffer solution: three (methylol) aminomethanes；Tromethamine；N-tris hydroxymethyl aminomethane；Trishydroxymethylaminomethane；
Tris, English name: Tris (hydroxymethyl) aminomethane；
Step 3, pvdf membrane surface coat dopamine: by pvdf membrane cleaned in step 1 be impregnated into step 2 prepare it is more
In bar amine aqueous solution, at room temperature, dopamine is in the abundant one strata dopamine coat of autohemagglutination in pvdf membrane surface；
The preparation of step 4, aromatic polycarboxylic acyl chlorides organic solution: aromatic polycarboxylic acyl chlorides is dissolved into organic solution；
Step 5 is grafted aromatic polycarboxylic acyl chlorides from the pvdf membrane of poly-dopamine: by the PVDF of dopamine of autohemagglutination in step 3
In aromatic polycarboxylic acyl chlorides organic solution in film immersion to step 4, certain time is impregnated, aromatic polycarboxylic acyl chlorides can be grafted to
From the pvdf membrane of poly-dopamine；
The preparation of step 6, amido modified titania nanoparticles: by nano-titanium dioxide, toluene and end band ammonia
In a round bottom flask, ultrasonic disperse heats certain temperature and the certain time that flows back, then under stiring to the silane coupling agent of base
Toluene is distilled out, is finally washed with EtOH Sonicate, amido modified titanium dioxide nanoparticle can be obtained；
Step 7, amido modified titania nanoparticles are grafted on pvdf membrane: the grafting that will be prepared in step 5
In the organic dispersions for the amido modified titania nanoparticles that the film immersion of aromatic polycarboxylic acyl chlorides is prepared into step 6,
Certain time is impregnated, nano-titanium dioxide is can be obtained and is grafted on pvdf membrane and prepare compound PVDF ultrafiltration membrane.
Preferably, the mass concentration of the dopamine solution is 0.3~3.0g/ in the step 2 of above-mentioned preparation method
L.It selects more preferably, the mass concentration of dopamine solution is 1.5~2.0g/L.
Preferably, in the step 3 of above-mentioned preparation method, time 6 that the pvdf membrane impregnates in dopamine solution
~for 24 hours.
Preferably, the aromatic polycarboxylic acyl chlorides is pyromellitic trimethylsilyl chloride in the step 4 of above-mentioned preparation method, or
Phthalyl chloride or paraphthaloyl chloride, the weight concentration of aromatic polycarboxylic acyl chlorides is 0.1~0.8wt% in organic solution.As
It more preferably selects, the aromatic polycarboxylic acyl chlorides is pyromellitic trimethylsilyl chloride, and the weight concentration of aromatic polycarboxylic acyl chlorides is in organic solution
0.2~0.5wt%.
Preferably, organic solvent used in the organic solution is Isobar in the step 4 of above-mentioned preparation methodG,
Or n-hexane or normal heptane or dodecane or trifluorotrichloroethane.Select more preferably, the organic solution it is organic molten
Agent is IsobarG。
Preferably, in the step 5 of above-mentioned preparation method, the pvdf membrane of autohemagglutination dopamine is in aromatic polycarboxylic acyl
15~120S of dip time in chlorine organic solution.
Preferably, silane coupling agent of the end with amino is 3- aminopropyl in the step 6 of above-mentioned preparation method
Triethoxysilane or 3- aminopropyl trimethoxysilane.50~150 DEG C of the heating temperature, return time 6~for 24 hours.
Preferably, the organic dispersions are amido modified nanometer titanium dioxides in the step 7 of above-mentioned preparation method
Titanium particle ultrasonic disperse is to IsobarGOr in toluene solution, amido modified titanium dioxide nanoparticle in organic dispersions
Weight concentration is 0.04~0.10wt%.It selects more preferably, the organic dispersions are amido modified nanometer titanium dioxides
Titanium particle ultrasonic disperse is to IsobarGIn, the weight concentration of amido modified titanium dioxide nanoparticle is in organic dispersions
0.08~0.10wt%.
Preferably, the pvdf membrane for being grafted aromatic polycarboxylic acyl chlorides is impregnated into the step 7 of above-mentioned preparation method
Dip time in the organic dispersions of amido modified titanium dioxide nanoparticle is 5~20min.
Preferably, the compound PVDF ultrafiltration membrane is plate membrane or hollow-fibre membrane or tubular membrane.
The invention has the following advantages:
Autohemagglutination of the present invention by dopamine on pvdf membrane surface forms a poly-dopamine coat, because dopamine has
Some hydroxyls and amino isoreactivity group, then by being used as graft in pyromellitic trimethylsilyl chloride, by amido modified nanometer two
Titanium oxide is grafted to surface from the pvdf membrane of poly-dopamine, so that the hydrophily of pvdf membrane greatly improves, to improve
The antifouling property of pvdf membrane；When pollutant adsorbs or deposits, nano-titanium dioxide under ultraviolet radiation, urged by pollutant
Change degradation to reach the self-cleaning purpose of film light.
Detailed description of the invention
Process schematic of Fig. 1 dopamine in one strata dopamine coat of pvdf membrane surface autohemagglutination
Fig. 2 aromatic polycarboxylic acyl chlorides is grafted to from the process schematic on the pvdf membrane of poly-dopamine
The preparation process schematic diagram of Fig. 3 amido modified titania nanoparticles
Fig. 4 amido modified titania nanoparticles are grafted to schematic diagram on pvdf membrane
Specific embodiment:
The present invention is further illustrated below with reference to example, but is not any restrictions of the content of present invention range.
Embodiment 1
The pvdf membrane of commodity is immersed in dehydrated alcohol for 24 hours by step 1, is then cleaned repeatedly with deionized water, is obtained clear
Wash the pvdf membrane of rear commodity.
Embodiment 2
The pvdf membrane of commodity is immersed in dehydrated alcohol for 24 hours by step 1, is then cleaned repeatedly with deionized water；
2g/L dopamine is dissolved into the Tris-HCI buffer solution that pH value is 8.5 by step 2；
Pvdf membrane cleaned in step 1 is impregnated into the dopamine solution that step 2 is prepared by step 3, is soaked at room temperature
Stain 12h, dopamine obtain the pvdf membrane of coating poly-dopamine in the abundant one strata dopamine coat of autohemagglutination in pvdf membrane surface,
Preparation process is as shown in Figure 1.
Embodiment 3
The pvdf membrane of commodity is immersed in dehydrated alcohol for 24 hours by step 1, is then cleaned repeatedly with deionized water；
2g/L dopamine is dissolved into the Tris-HCI buffer solution that pH value is 8.5 by step 2；
Pvdf membrane cleaned in step 1 is impregnated into the dopamine solution that step 2 is prepared by step 3, is soaked at room temperature
Stain 12h, dopamine obtain the pvdf membrane of coating poly-dopamine in the abundant one strata dopamine coat of autohemagglutination in pvdf membrane surface；
Pyromellitic trimethylsilyl chloride is dissolved into Isobar by step 4GIn solution, pyromellitic trimethylsilyl chloride is in IsobarGIn solution
Weight concentration is 0.5wt%；
The pvdf membrane of the dopamine of autohemagglutination in step 3 is impregnated into the pyromellitic trimethylsilyl chloride in step 4 by step 5
IsobarGIn solution, 60S is impregnated, pyromellitic trimethylsilyl chloride can be grafted to from the pvdf membrane of poly-dopamine；Preparation process is such as
Shown in Fig. 2；
Step 6, by 6.0g particle size range in 30 ± 5nm titanium dioxide nanoparticle, 120mL toluene and 24mL3- aminopropyl
In a round bottom flask, ultrasonic disperse 30min heats and is stirred at reflux for 24 hours at 115 DEG C, then distills out first triethoxysilane
Benzene is finally washed with EtOH Sonicate, and amido modified titanium dioxide nanoparticle can be obtained；Preparation process is as shown in Figure 3；
The pvdf membrane of the grafting pyromellitic trimethylsilyl chloride prepared in step 5 is impregnated into the amino synthesized in step 6 by step 7
The Isobar of the titania nanoparticles of modificationGIn dispersion liquid, IsobarGAmido modified nano titania in dispersion liquid
The weight concentration 0.04wt% of particle, impregnates 10min in dispersion liquid, can be obtained nano-titanium dioxide and is grafted on pvdf membrane
Compound PVDF ultrafiltration membrane is prepared, grafting process is as shown in Figure 4.
Embodiment 4
Step 1~6 are with embodiment 3, Isobar in step 7GAmido modified titania nanoparticles in dispersion liquid
Weight concentration 0.06wt%.
Embodiment 5
Step 1~6 are with embodiment 3, Isobar in step 7GAmido modified titania nanoparticles in dispersion liquid
Weight concentration 0.08wt%.
Embodiment 6
Step 1~6 are with embodiment 3, Isobar in step 7GAmido modified titania nanoparticles in dispersion liquid
Weight concentration 0.10wt%.
Embodiment 7
Step 1~6 are with embodiment 3, Isobar in step 7GAmido modified titania nanoparticles in dispersion liquid
Weight concentration 0.08wt% impregnates 5min in dispersion liquid.
Embodiment 8
Step 1~6 are with embodiment 3, Isobar in step 7GAmido modified titania nanoparticles in dispersion liquid
Weight concentration 0.08wt% impregnates 15min in dispersion liquid.
Embodiment 9
Step 1~6 are with embodiment 3, Isobar in step 7GAmido modified titania nanoparticles in dispersion liquid
Weight concentration 0.08wt% impregnates 20min in dispersion liquid.
The evaluation of compound membrane separating property and antifouling property prepared by the present invention:
Water flux (J) is defined as: under certain operating conditions, through the water of per membrane area (A) in the unit time (t)
Volume (V), unit L/m2H (is denoted as LMH).Specific formula for calculation is as follows:
JW1And JW2For the pure water flux (J that the testing time is 1 hourW1Represent the pure of the cephacoria of protein solution flux test
Water flux, and JW2After the test of protein solution flux, pure water flux after seeking Membrane cleaning).
Composite membrane is as follows to the calculation formula of the rejection (R) of BSA protein:
CPAnd CPThe concentration of protein respectively in permeate and feeding liquid, concentration use ultraviolet-visible spectrophotometer
It is measured at 280nm.
Flux recovery rate (FRw), gross contamination parameter (Rt), reversible membrane fouling parameter (Rr) and irreversible membrane fouling parameter (Rir)
Etc. parameters be used to the antifouling property of evaluated for film, specific formula for calculation is as follows:
Table 1: the more compound PVDF ultrafiltration membrane separating property of Examples 1 to 9 and antifouling property:
As a result compare: IsobarGThe weight concentration 0.08wt% of amido modified titania nanoparticles in dispersion liquid,
Impregnate 10min in dispersion liquid, the flux of the compound PVDF ultrafiltration membrane of preparation, restorability, rejection and antifouling property are best.
Embodiment 10
The film prepared in embodiment 5 is applied in the oily waste water of the rust preventing emulsion compounding of 1.0g/L, the retention of film
Rate is 99.5%, and the restorability of film is 83%.The film that the restorability is 83% is irradiated into 30min under ultraviolet light, film
Restorability has reached 100%.It has absolutely proved and has changed compound PVDF ultrafiltration membrane with light clean-up performance.
The above, only the invention patent preferred embodiment cannot be limited the scope of implementation of the present invention successively, i.e.,
According to the invention patent scope and specification content equivalence changes and modification, all should belong in the range of the present invention covers.
Claims (8)
1. a kind of preparation method of compound PVDF ultrafiltration membrane, which comprises the following steps:
Step 1, the pvdf membrane for cleaning commodity: the pvdf membrane of commodity is immersed in dehydrated alcohol for 24 hours, then anti-with deionized water
Multiple cleaning；
Step 2 prepares dopamine solution: dopamine is dissolved into the Tris-HCI buffer solution that pH value is 8.5；The DOPA
The mass concentration of amine aqueous solution is 0.3~3g/L；
Step 3, pvdf membrane surface coat dopamine: pvdf membrane cleaned in step 1 is impregnated into the DOPA prepared in step 2
In amine aqueous solution, at room temperature, dopamine is in the abundant one strata dopamine coat of autohemagglutination in pvdf membrane surface；The pvdf membrane exists
The time 6 impregnated in dopamine solution~for 24 hours；
The preparation of step 4, aromatic polycarboxylic acyl chlorides organic solution: aromatic polycarboxylic acyl chlorides is dissolved into organic solution；The virtue
Fragrant polynary acyl chlorides is pyromellitic trimethylsilyl chloride, m-phthaloyl chloride or paraphthaloyl chloride, aromatic polycarboxylic acyl chlorides in organic solution
Weight concentration is 0.1~0.8wt%；
Step 5 is grafted aromatic polycarboxylic acyl chlorides from the pvdf membrane of poly-dopamine: the pvdf membrane of the dopamine of autohemagglutination in step 3 is soaked
In aromatic polycarboxylic acyl chlorides organic solution in stain to step 4, certain time is impregnated, aromatic polycarboxylic acyl chlorides can be grafted to autohemagglutination
On the pvdf membrane of dopamine；Organic solvent used in the organic solution is n-hexane, normal heptane, dodecane or trifluoro three
Chloroethanes.
The preparation of step 6, amido modified titania nanoparticles: by nano-titanium dioxide, toluene and end with amino
In a round bottom flask, ultrasonic disperse heats certain temperature and the certain time that flows back, then distills silane coupling agent under stiring
Toluene out is finally washed with EtOH Sonicate, and amido modified titanium dioxide nanoparticle can be obtained；
Step 7, amido modified titania nanoparticles are grafted on pvdf membrane: by the grafting prepared in step 5 fragrance
In the organic dispersions for the amido modified titania nanoparticles that the film immersion of polynary acyl chlorides is prepared into step 6, dipping
Certain time, can be obtained nano-titanium dioxide and is grafted on pvdf membrane and prepare compound PVDF ultrafiltration membrane, organic dispersion
Liquid is amido modified titanium dioxide nanoparticle ultrasonic disperse into toluene solution, amido modified nanometer in organic dispersions
The weight concentration of titanium dioxide granule is 0.04~0.10wt%.
2. preparation method according to claim 1, it is characterised in that the mass concentration of dopamine solution described in step 2
For 1.5~2.0g/L.
3. preparation method according to claim 1, which is characterized in that aromatic polycarboxylic acyl chlorides described in step 4 is equal benzene
Three formyl chlorides, the weight concentration of aromatic polycarboxylic acyl chlorides is 0.2~0.5wt% in organic solution.
4. preparation method according to claim 1, it is characterised in that the pvdf membrane of dopamine of autohemagglutination described in step 5
15~120S of dip time in aromatic polycarboxylic acyl chlorides organic solution.
5. preparation method according to claim 1, it is characterised in that silane coupling agent of the end described in step 6 with amino
It is 3- aminopropyl triethoxysilane or 3- aminopropyl trimethoxysilane.
6. preparation method according to claim 1, it is characterised in that 50~150 DEG C of heating temperature described in step 6, institute
The return time 6 stated~for 24 hours.
7. preparation method according to claim 1, it is characterised in that be grafted aromatic polycarboxylic acyl chlorides described in step 7
The dip time that pvdf membrane is impregnated into the organic dispersions of amido modified titanium dioxide nanoparticle is 5~20min.
8. preparation method according to claim 1, it is characterised in that the compound PVDF ultrafiltration membrane is plate membrane, or in
Empty fiber membrane or tubular membrane.
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| CN118022556B (en) * | 2024-04-12 | 2024-06-11 | 四川大学 | CuZn-C-loaded PEI modified PVDF self-cleaning film and preparation method and application thereof |
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