CN108392987B - A kind of anti-protein-contamination ultrafiltration membrane and preparation method that hydrogel is modified - Google Patents
A kind of anti-protein-contamination ultrafiltration membrane and preparation method that hydrogel is modified Download PDFInfo
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- CN108392987B CN108392987B CN201810216009.4A CN201810216009A CN108392987B CN 108392987 B CN108392987 B CN 108392987B CN 201810216009 A CN201810216009 A CN 201810216009A CN 108392987 B CN108392987 B CN 108392987B
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- 239000012528 membrane Substances 0.000 title claims abstract description 47
- 238000011109 contamination Methods 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000017 hydrogel Substances 0.000 title claims abstract description 8
- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 78
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002033 PVDF binder Substances 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 10
- ZLXPLDLEBORRPT-UHFFFAOYSA-M [NH4+].[Fe+].[O-]S([O-])(=O)=O Chemical compound [NH4+].[Fe+].[O-]S([O-])(=O)=O ZLXPLDLEBORRPT-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 230000002285 radioactive effect Effects 0.000 claims abstract description 5
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims abstract description 4
- 239000003112 inhibitor Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 210000004379 membrane Anatomy 0.000 claims description 37
- LZCXCXDOGAEFQX-UHFFFAOYSA-N N-Acryloylglycine Chemical compound OC(=O)CNC(=O)C=C LZCXCXDOGAEFQX-UHFFFAOYSA-N 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000003708 ampul Substances 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012965 benzophenone Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 8
- 229920002554 vinyl polymer Polymers 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003287 optical effect Effects 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 210000002469 basement membrane Anatomy 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- BEBCJVAWIBVWNZ-UHFFFAOYSA-N glycinamide Chemical compound NCC(N)=O BEBCJVAWIBVWNZ-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 238000010521 absorption reaction Methods 0.000 claims 1
- UMEAURNTRYCPNR-UHFFFAOYSA-N azane;iron(2+) Chemical compound N.[Fe+2] UMEAURNTRYCPNR-UHFFFAOYSA-N 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 19
- 239000000499 gel Substances 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 9
- 239000003431 cross linking reagent Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 3
- 150000001336 alkenes Chemical class 0.000 abstract description 2
- 238000010382 chemical cross-linking Methods 0.000 abstract description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 230000010148 water-pollination Effects 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 102000004169 proteins and genes Human genes 0.000 description 5
- 108090000623 proteins and genes Proteins 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000012460 protein solution Substances 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- WKNMKGVLOWGGOU-UHFFFAOYSA-N 2-aminoacetamide;hydron;chloride Chemical compound Cl.NCC(N)=O WKNMKGVLOWGGOU-UHFFFAOYSA-N 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- -1 acryloyl Amine Chemical class 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 235000010410 calcium alginate Nutrition 0.000 description 1
- 239000000648 calcium alginate Substances 0.000 description 1
- 229960002681 calcium alginate Drugs 0.000 description 1
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000029052 metamorphosis Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- FTQWRYSLUYAIRQ-UHFFFAOYSA-N n-[(octadecanoylamino)methyl]octadecanamide Chemical group CCCCCCCCCCCCCCCCCC(=O)NCNC(=O)CCCCCCCCCCCCCCCCC FTQWRYSLUYAIRQ-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- WOMAZEJKVZLLFE-UHFFFAOYSA-N propionylglycine Chemical compound CCC(=O)NCC(O)=O WOMAZEJKVZLLFE-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229940032021 tetramune Drugs 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
Classifications
-
- 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
-
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/12—Adsorbents being present on the surface of the membranes or in the pores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a kind of modified anti-protein-contamination seperation films and preparation method thereof of hydrogel.The present invention contains the alkenes substance (CH of multiamide group with side chain2=CH (CONH2)n, 1 < n < 5) and it is that monomer, using water and methanol as solvent, is grafted using iron ammonium sulfate as polymerization inhibitor by ultraviolet radioactive, it is obtained on PVDF ultrafiltration membrane surface a kind of with hydrophilic gel layer.Modified film surface initial contact angle drops to 55 ° or so from initial 120 °, and can reach 0 ° within 10-12s, and flux recovery rate reaches 90%-99%.Separation membrane surface prepared by the present invention has excellent anti-protein contamination ability, and biocompatibility is preferable, compared with traditional method that hydrogel is coated in film surface, the gel layer stability of grafting on the surface of the film is more excellent, preparation method is simple, without adding chemical cross-linking agent, performance is stablized, easy cleaning.
Description
Technical field
The invention belongs to polymeric membrane for separation field, the anti-protein-contamination ultrafiltration membrane modified about a kind of hydrogel and its
Preparation method.
Background technique
Compared with traditional separation method, membrane separation technique has many advantages, such as high efficiency, low energy consumption, without phase-change.Wherein gather
Vinylidene (PVDF) film has preferable mechanical performance, resistant to chemical etching and preferable thermal stability, so it is in film work
There is biggish attraction in industry and had a wide range of applications in terms of liquid separation.But due to pvdf membrane surface fluorine atom
Presence, surface is presented biggish hydrophobic performance, easily adsorbs to protein so as to cause it.When pvdf membrane is applied to life
When Tetramune separates, protein is easy to adsorb in film surface, and film permeation flux is caused to be decayed.Thus often more to renew
Film cleans film surface, to increase separation costs.Therefore, how to design and prepare pollution-resistant membrane material raising film
Anti- protein contamination ability and low energy consumption high-efficiency handle sewage, it has also become the important research of current membrane technology and application field
Project.
Around the anti-protein-contamination ability for how improving pvdf membrane surface, domestic and foreign scholars, which have been carried out, largely to be ground
Study carefully, and explored three kinds of anti-protein-contamination mechanism generally accepted, including steric hindrance is theoretical, surface charge theory with
And aquation shelf theory, presently mainly increase the anti-protein contamination ability of film surface by increasing the hydrophily of film surface.One
As for, film surface hydrophily is better, and the ability of anti-protein-contamination is stronger.Hydrophily is largely the survey by contact angle
To characterize, contact angle is smaller to show that hydrophily is better for examination.At the same time, flux recovery rate is also that characterization film surface anti-protein is dirty
One main indicator of dye ability.Flux recovery rate is obtained from the flux loop test of pure water and protein solution, flux
Recovery rate is higher, and the anti-protein-contamination ability for showing film is stronger.
Group currently used for hydrophilic modifying mainly includes carboxyl, hydroxyl, sulfonic group etc..Wherein amide group has relatively prominent
Hydrophily out, many scholars have conducted extensive research amide group Modified Membrane.Liu Lifen etc. is in patent of invention (China
Patent, the patent No.: CN2012100851640) in disclose a kind of auto polymerization by dopamine in titanium dioxide nano-particle
Surface forms active poly-dopamine composite layer, the technology being then blended using this nanoparticle with PVDF, and blend film resists
Pollutant performance has obtained very big promotion.Yang Xuanxuan etc. (radiation research and radiation process journal, 29,4:209-213) is by acryloyl
Amine is grafted on PVDF powder, then knifing, and flux recovery rate increases to 80% from 51%, and anti-protein-contamination performance obtains
Very big promotion.Huyan Shi etc. (Journal of Membrane Science, 2016,496:39-47) is by PVDF
Hollow fiber membrane surface coating polyethylene imines, contact angle drop to 10 ° from 80 °, and flux recovery rate reaches 94%, this illustrates it
Hydrophily and resistance protein adsorption capacity have obtained very big promotion.(the Applied Surface such as Xushan Wang
Science, 2017,496:546-556) in film surface grafting polyethyleneimine, and by reacting with glycidol to its hydroxyl
Base.Surface contact angle drops to 38 ° from 137 °, and flux recovery rate increases to 80% from 40%.(the Reactive such as Guili Zhao
And Functional Polymers, 2015,97:19-29) film surface is arrived by polyisobutylene is acid amide-grafted, contact angle is from 106 °
50 ° are dropped to, flux recovery rate reaches 91.59%.
In recent years, more and more scholars carry out hydrophilic modifying to film surface using hydrogel.Hydrogel has hydrophilic residual
Base, strand can form relatively firm water by being physically or chemically cross-linked to form tridimensional network in separation membrane surface
Change layer, there is more excellent hydrophily.(the Journal of Industrial and Engineering such as Sunjie Xu
Chemistry, 2018,58:179-188) calcium alginate gel is coated on polymer film, modified flux recovery is reachable
99%.Weilong Song etc. (Journal of Membrane Science, 2018,550:266-277) will be a kind of novel
Organic silicon sol-gel coating is on pvdf membrane, and contact angle can be down to 35 ° from 73 °, and flux recovery rate may be up to 94%.Yutao
Hu etc. (Journal of Membrane Science, 2018,545:250-258) is by tetraethyl orthosilicate gel coating to water
Enhance the ability of hydrophily and anti-protein-contamination in the PAN film of solution, wherein modified film surface contact angle is about 38 °,
Flux recovery rate is up to 91.3%.The studies above is mostly by coating method, by gel molecular characteristic group and film surface
Forming hydrogen bond or electrostatic interaction enhances film surface hydrophily.However, the disadvantage of this method is that it cannot be guaranteed that for a long time
The stability of gel layer, gel easily fall off from film surface when filtering, to seriously affect the effect of anti-protein-contamination.So such as
The stability of what enhancing gel layer is a problem for needing to solve.
Graft modification is to improve a polymer-modified effective ways in film surface stability.Graft-modification method has very
It is a variety of, including plasma initiation grafting, atom transfer radical polymerization grafting, it is square that alkali process causes free radical polymerization grafting etc.
Method.In these methods, ultraviolet radioactive initiation grafting has the advantages that more prominent, its equipment is simple, and operating cost is low, in addition
For ultraviolet light compared to for high-energy radiation, penetration capacity is poor, so UV initiated grafting reaction can not destroy basement membrane, keeps
The original preferable mechanical performance of pvdf membrane, high temperature resistance etc..However due to the limitation of Gel formation mechanism, it is difficult to coagulate
Glue is grafted to film surface, or water soluble polymer formation gel is loaded to film surface, it is also necessary to add crosslinking agent, grasp in this way
Make complicated, increased costs.
The present invention has the vinyl monomer (CH of multiamide group using side chain2=CH (CONH2)n, 1 < n < 5) and it is to be modified
Substance, such compound side group have a multiamide group, intramolecular and intermolecular can be self-assembly of more hydrogen bonds physical crosslinking
Structure, the free hydrophilic radical in part is easy on strand and water molecules, can adsorb a large amount of water in the network system, whole
A three-dimensional network system is not easily dissolved into water mechanical strength with higher at normal temperature, therefore is grafted on separation membrane surface
When, stable hydrated sheath can be kept for a long time, further increased protein solution separating effect and prolonged the service life.This
Invention passes through ultraviolet radioactive first and forms free radical on pvdf membrane surface, and free radical causes the vinyl monomer containing multiamide group
It is grafted to film surface, and generates new free radical, continues to cause more monomer polymerizations, so that polymer is grafted to film table
Face.Corresponding polymer can independently be filled by the hydrogen bond of molecule interchain in the case where crosslinking agent is not added and form physical gel
(referring to Figure of description 1).In room temperature aqueous solution, which can keep stable cross-linked structure；And at 90 DEG C
In above high temperature aqueous solution, which also has the characteristic of self-healing, facilitates the reparation to film surface mechanical damage.
The grafting gel layer can effectively improve the anti-protein-contamination ability of film surface, while be convenient for the cleaning of surface contaminant again.
It is compared with the traditional method, film prepared by the present invention has many advantages, such as easy to operate, significant effect.The present invention gives separation membrane surface parent
It is watersoluble modified that a kind of new thinking is provided, substance with similar structures (vinyl monomer that side chain contains multiamide group) or
The compound for forming cross-linked network structure can be independently filled by intermolecular physics hydrogen bond, can be used for that film surface is hydrophilic to be changed
Property.
Summary of the invention
The present invention has the vinyl monomer of multiamide group as modified compound (CH using side chain2=CH (CONH2)n, 1 < n
< 5), using benzophenone as photoinitiator, using iron ammonium sulfate as polymerization inhibitor, using methanol and distilled water as solvent, be with PVDF
Basement membrane forms free radical on pvdf membrane surface by ultraviolet radioactive, causes the vinyl monomer containing multiamide group and be grafted to film
Surface, and new free radical is generated, cause more monomer polymerizations, so that polymer is grafted to film surface.The above is anti-
The preparation step of protein contamination seperation film is as follows:
The preparation of 1.N- acryloyl glycine amide (side chain contains bisamide group) is according to Xiyang Dai etc.
The method that (Advanced Material, 23,27:3566-3571) is proposed, preparation step are as follows:
1) glycyl amide hydrochloride, deionized water, potassium carbonate and ether are added sequentially to be placed in ice-water bath (0 DEG C) three
In neck glass flask；
2) mixed liquor of the constant pressure separatory funnel to above-mentioned mixed solution and dripping ether and acryloyl chloride is used, later in room
It is futher stirred under temperature 4 hours；
3) 6mol/L HCl is added dropwise into the mixture after above-mentioned reaction, adjusts pH to 2；
4) said mixture is washed three times with 150mL ether, removes remaining ether using rotary evaporation；
5) pH of mixture solution is adjusted to neutrality with 2mol/L NaOH, it is freeze-dried to obtain crude product；
6) crude product (N- acryloyl glycine amide and potassium chloride etc.) is used into 150mL ethyl alcohol/methanol mixed solution (4/1, V/
V) washing removes organic salt three times；
7) rotary evaporation removes ethyl alcohol and methanol, and remaining mixture is recrystallized at 0 DEG C, obtains purification N- propionyl
Glycine amide is dried in vacuo.
The additional amount of glycyl amide hydrochloride is 6.30g, 0.05706mol in the step 1)；Deionization additional amount is
6mL；The additional amount of cold potassium carbonate is 33.6mL, 2molL-1；Ether additional amount is 18mL；Time for adding is 1h；
Ether additional amount is respectively 24mL in the step 2)；Acryloyl chloride additional amount is 5.70g.
2. the preparation step of anti-protein-contamination ultrafiltration membrane is as follows:
1) PVDF original film is placed in methanol solution and is cleaned；
2) pvdf membrane after cleaning is soaked in the methanol solution containing benzophenone, naturally dry is taken out after 1h；
3) it by the N- acryloyl glycine amide of certain mass, is dissolved in containing deionized water, methanol and iron ammonium sulfate
Solution in, then mixed liquor is poured into quartz ampoule, lead to nitrogen 0.5h, immerse the pvdf membrane dried, be sealed；
4) quartz ampoule after sealing is put and is irradiated in the UV lamp after a certain period of time, takes the film out, with methanol and water-soluble
Liquid cleans film, is dried in vacuo spare.
Above-mentioned steps 1) in PVDF original film can be commercial membranes or homemade film, pore size is 0.1 μm of -0.45 μ
M, film upper surface area are 15-20cm2；
Above-mentioned steps 2) in benzophenone concentration be 0.1-1mol/L；
Above-mentioned steps 3) in N- acryloyl glycine amide quality be 0.1-1.5g, methanol and distilled water ratio are 1: 3-1: 6,
N- acryloyl glycine amide and solution quality ratio are 1: 25-1: 400, and iron ammonium sulfate and NAGA mass ratio are 1: 2-1: 6；
Above-mentioned steps 4) under ultraviolet lamp optical density be 3-10J/cm2, radiated time 5-60min.
The present invention has following advantageous effects: film surface hydrophily improves, the enhancing of anti-protein adsorption capacity, and raw
Object compatibility is preferable, easy to operate, does not need addition chemical cross-linking agent, and gel layer structure and membrane separating property are stablized, and is easy clear
It washes.This belongs to a kind of novel anti-protein-contamination seperation film.
Detailed description of the invention
Fig. 1 is the hydrogen bond schematic diagram between generation strand after pvdf membrane grafting multiamide vinyl monomer.
Fig. 2 is that the N- acryloyl glycine amide Modified Membrane surface contact angle prepared in case study on implementation 2 changes over time figure.
Fig. 3 is pure water-protein solution flux circulation of the N- acryloyl glycine amide Modified Membrane prepared in case study on implementation 2
Test chart.
Fig. 4 is that the N- acryloyl glycine amide Modified Membrane prepared in case study on implementation 2 is passed through ultrasound 30min and persistently led to for 24 hours
After measuring examination, film surface metamorphosis figure.Wherein (a) is the original scan electron microscope of Modified Membrane, (b) for by ultrasound 30min
Scanning electron microscope (SEM) photograph afterwards (c) is to continue scanning electron microscope (SEM) photograph after flux test for 24 hours.
Specific embodiment
Embodiment 1:
(1) synthesis of N- acryloyl glycine amide:
1) glycyl amide hydrochloride (6.30g, 0.05706mol), 6mL deionized water, the cold potassium carbonate of 33.6mL (2mol/L)
It is added in three neck glass flasks (volume 100mL, ice water mixing bath) with 18mL cold ether；
2) mixing of ether (24mL) and acryloyl chloride (5.70g) is added dropwise into above-mentioned mixed liquor using constant pressure separatory funnel
Solution, 1h are dripped, and are continuously stirred at room temperature 4 hours；
3) 6mol/L HCl is added dropwise into the mixture after above-mentioned reaction, adjusts pH to 2；
4) said mixture is washed three times with 150mL ether, remaining ether is removed using rotary evaporation；
5) pH of mixture solution is adjusted to neutrality with 2mol/L NaOH, it is freeze-dried to obtain crude product；
6) crude product (N- acryloyl glycine amide and potassium chloride etc.) is used into 150mL ethyl alcohol/methanol mixed solution (4/1, V/
V) washing removes organic salt three times；
7) rotary evaporation removes ethyl alcohol and methanol, and remaining mixture is recrystallized at 0 DEG C, the N- third refined
Alkene acyl glycine amide, is dried in vacuo.
(2) preparation of anti-protein-contamination seperation film:
It 1) is 0.1 μm by aperture, upper surface area 15cm2The former film of PVDF business be placed in methanol solution carry out it is clear
It washes；
2) pvdf membrane after cleaning is soaked in the methanol solution containing benzophenone (1mol/L), nature is taken out after 1h
It dries；
3) 1g N- acryloyl glycine amide is weighed, 3g iron ammonium sulfate, 8mL methanol and 42mL distilled water are made into mixing
Solution is transferred in quartz ampoule later, leads to nitrogen 0.5h, and the pvdf membrane dried is immersed, is sealed；
4) quartz ampoule after sealing is placed on optical density is 4J/cm2Ultraviolet lamp under, irradiation 50min then take the film out
It is cleaned, is dried in vacuo spare with methanol and aqueous solution.
Embodiment 2:
(1) synthesis of N- acryloyl glycine amide: with embodiment 1.
(2) preparation of anti-protein-contamination seperation film:
It 1) is 0.22 μm by aperture, upper surface area 18cm2The former film of PVDF business be placed in methanol solution carry out it is clear
It washes；
2) pvdf membrane after cleaning is soaked in the methanol solution containing benzophenone (0.7mol/L), is taken out certainly after 1h
So dry；
3) 0.4g N- acryloyl glycine amide is weighed, 0.1g iron ammonium sulfate, 11mL methanol and 39mL distilled water are made into
Mixed solution is transferred in quartz ampoule later, leads to nitrogen 0.5h, and the pvdf membrane dried is immersed, is sealed；
4) quartz ampoule after sealing is placed on optical density is 6J/cm235min is irradiated under ultraviolet lamp.Then film is taken
It is cleaned out with methanol and aqueous solution.
Experimental comparison's example:
It is 0.22 μm by average pore size, top surface area 18cm2The former film of PVDF business be placed in methanol solution carry out it is clear
It washes, is then dried in vacuo, PVDF blank ultrafiltration membrane needed for obtaining this experiment.
Experiment effect:
The present invention is directed to the problem of existing seperation film anti-protein adsorption capacity difference, and novel anti-protein is prepared in design
Pollute PVDF ultrafiltration membrane.Tested using the sample that case study on implementation 2 obtains, find: (1) pvdf membrane surface initial contact angle from
121 ° drop to 55 °, and with the variation of time, contact angle can drop to 0 ° (referring to Figure of description 2) within 11s, say
The hydrophily on bright pvdf membrane surface is greatly improved；(2) protein solution is carried out to film and pure water solution flux recycles
Test, for blank film after three loop tests, flux recovery rate falls below 15.1% from 46.2%, and passes through N- acryloyl
Glycine amide is modified, and flux recovery rate maintains always 99% or more (referring to Figure of description 3), this illustrate its have compared with
Excellent anti-protein-contamination ability；(3) after Modified Membrane continues flux test by ultrasonic 30min and for 24 hours, weight and fenestra
There is no substantially changeing to illustrate that gel layer has more excellent stability (referring to Figure of description 4) for form.
Claims (9)
1. a kind of preparation method of the modified anti-protein-contamination ultrafiltration membrane of hydrogel, it is characterised in that contain multiamide base with side chain
Vinyl monomer (the CH of group2=CH (CONH2)n, 1 < n < 5) and it is modified material, using benzophenone as photoinitiator, with sulfuric acid Asia
Iron ammonium is polymerization inhibitor, using methanol and distilled water as solvent, with Kynoar (PVDF) for basement membrane, by ultraviolet radioactive in PVDF
Film surface forms free radical, causes the vinyl monomer containing multiamide group and is grafted to film surface, and generates new free radical,
Cause more monomer polymerizations, so that polymer is grafted to film surface, obtains with the good separation of anti-protein absorption property
Film, specific preparation process is as follows:
1) PVDF original film is placed in methanol solution and is cleaned；
2) pvdf membrane after cleaning is soaked in the methanol solution containing benzophenone, naturally dry is taken out after 1h；
3) by the N- acryloyl glycine amide of certain mass, be dissolved in containing deionized water, methanol and iron ammonium sulfate it is molten
In liquid, then mixed liquor is poured into quartz ampoule, leads to nitrogen 0.5h, immerses the pvdf membrane dried, be sealed；
4) quartz ampoule after sealing is put to be irradiated after a certain period of time in the UV lamp, is taken the film out, with methanol and aqueous solution pair
Film is cleaned, and is dried in vacuo spare.
2. preparation method described according to claim 1, it is characterised in that: the PVDF original film in the step 1) be commercial membranes or
The homemade film of person.Pore size is 0.1-0.45 μm, and film upper surface area is 15-20cm2。
3. preparation method described according to claim 1, it is characterised in that: benzophenone concentration is 0.1- in the step 2)
1mol/L。
4. preparation method described according to claim 1, it is characterised in that: N- acryloyl glycine amide quality in the step 3)
For 0.1-1.5g.
5. preparation method described according to claim 1, it is characterised in that: methanol and distilled water ratio are 1 in the step 3):
3-1∶6。
6. preparation method described according to claim 1, it is characterised in that: in the step 3) N- acryloyl glycine amide with it is molten
Liquid mass ratio is 1: 25-1: 400.
7. preparation method described according to claim 1, it is characterised in that: iron ammonium sulfate and N- acryloyl in the step 3)
Glycine amide mass ratio is 1: 2-1: 6.
8. preparation method described according to claim 1, it is characterised in that: optical density is 3- under ultraviolet lamp in the step 4)
10J/cm2。
9. preparation method described according to claim 1, it is characterised in that: radiated time is 5-60min in the step 4).
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| CN110124533B (en) * | 2019-06-17 | 2021-05-28 | 天津工业大学 | Gel microsphere modified anti-pollution oil-water separation ultrafiltration membrane and preparation method thereof |
| CN111530310B (en) * | 2020-04-30 | 2022-03-22 | 曲靖师范学院 | Preparation method of reversed-phase high-critical-dissolution-temperature type temperature-sensitive polyacrylonitrile separation membrane |
| CN112852009B (en) * | 2021-02-09 | 2023-10-31 | 深圳华源再生医学有限公司 | Method for modifying porous polymer film, modified porous polymer film, and medical article |
| CN116903202B (en) * | 2023-09-14 | 2023-11-24 | 上海联风气体有限公司 | Fluorine-containing wastewater treatment method |
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| CN104031282A (en) * | 2014-06-09 | 2014-09-10 | 吉安市青原区庆丰过滤器材有限公司 | Polyvinylidene fluoride (PVDF) microfiltration membrane surface light graft modification method |
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