CN106215722A - A kind of high temperature resistant composite nanometer filtering film of grafted graphene oxide coating and preparation method thereof - Google Patents
A kind of high temperature resistant composite nanometer filtering film of grafted graphene oxide coating and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000576 coating method Methods 0.000 title claims abstract description 22
- 239000011248 coating agent Substances 0.000 title claims abstract description 11
- 238000001914 filtration Methods 0.000 title abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 65
- 125000000524 functional group Chemical group 0.000 claims abstract description 37
- 239000012190 activator Substances 0.000 claims abstract description 30
- 239000012528 membrane Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- 230000004913 activation Effects 0.000 claims abstract description 14
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 9
- 210000000433 stratum disjunctum Anatomy 0.000 claims abstract description 9
- 239000007790 solid phase Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 229920002492 poly(sulfone) Polymers 0.000 claims description 15
- 239000004745 nonwoven fabric Substances 0.000 claims description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000003002 pH adjusting agent Substances 0.000 claims description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- 239000004094 surface-active agent Substances 0.000 claims description 8
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 7
- 238000007598 dipping method Methods 0.000 claims description 7
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 6
- -1 polypropylene Polymers 0.000 claims description 6
- 239000002352 surface water Substances 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 5
- JHJUUEHSAZXEEO-UHFFFAOYSA-M sodium;4-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=C(S([O-])(=O)=O)C=C1 JHJUUEHSAZXEEO-UHFFFAOYSA-M 0.000 claims description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 229910000071 diazene Inorganic materials 0.000 claims description 4
- JMGZBMRVDHKMKB-UHFFFAOYSA-L disodium;2-sulfobutanedioate Chemical compound [Na+].[Na+].OS(=O)(=O)C(C([O-])=O)CC([O-])=O JMGZBMRVDHKMKB-UHFFFAOYSA-L 0.000 claims description 4
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 claims description 3
- LQPUCRPHHIWEMI-UHFFFAOYSA-N C(CCCCCCCCCCC)C(C#N)(C)N.[Na] Chemical compound C(CCCCCCCCCCC)C(C#N)(C)N.[Na] LQPUCRPHHIWEMI-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 3
- 229920006221 acetate fiber Polymers 0.000 claims description 3
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002480 mineral oil Substances 0.000 claims description 3
- 235000010446 mineral oil Nutrition 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- KSAVQLQVUXSOCR-UHFFFAOYSA-M sodium lauroyl sarcosinate Chemical compound [Na+].CCCCCCCCCCCC(=O)N(C)CC([O-])=O KSAVQLQVUXSOCR-UHFFFAOYSA-M 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical group [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- OGGBYDPEZJVNHM-UHFFFAOYSA-N dodecanoate;hydron;potassium Chemical compound [K].CCCCCCCCCCCC(O)=O OGGBYDPEZJVNHM-UHFFFAOYSA-N 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 6
- 238000009472 formulation Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 75
- 239000010410 layer Substances 0.000 description 34
- 239000007788 liquid Substances 0.000 description 8
- FEKRFYZGYUTGRY-UHFFFAOYSA-N n'-ethylmethanediimine Chemical compound CCN=C=N FEKRFYZGYUTGRY-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000004907 flux Effects 0.000 description 7
- 238000000926 separation method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 4
- 238000002955 isolation Methods 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000012695 Interfacial polymerization Methods 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- 208000036626 Mental retardation Diseases 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002068 microbial inoculum Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 150000003900 succinic acid esters Chemical class 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 210000004885 white matter Anatomy 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
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/78—Graft polymers
-
- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
Abstract
The present invention relates to Nanofiltration-membrane technique field, especially a kind of high temperature resistant composite nanometer filtering film of grafted graphene oxide coating and preparation method thereof, after graphene oxide is dissolved in solvent, add polymer formulation polymer solution, again through traditional liquid-solid phase conversion method preparation containing graphene oxide porous polymer supporting layer, activation processing in conjunction with functional group's activator, make to be grafted into one layer of graphite oxide ene coatings between the stratum disjunctum and polymeric support layer of composite nanometer filtering film, and integrating step (3), A in step (4), B solution soaks modification, make the graphite oxide ene coatings can be with polymeric support layer, stratum disjunctum is mutually chemically bonded, improve the stability of composite nanometer filtering film, improve the resistance to elevated temperatures of composite nanometer filtering film.
Description
Technical field
The present invention relates to Nanofiltration-membrane technique field, especially a kind of high temperature resistant composite nanometer filtering film of grafted graphene oxide coating
And preparation method thereof.
Background technology
Membrance separation is a kind of novel isolation technics, compared with the isolation technics such as traditional distillation, rectification, has mental retardation
The advantages such as consumption, high separating efficiency, environmental protection.That filter membrane isolation technics power-actuated film of the Novel pressure between reverse osmosis and ultrafiltration
Isolation technics, it is generally higher than 90% to the rejection of bivalence or multivalent ion or the molecular weight organic molecule more than 200,
The Selective Separation to different material can be realized；Through being widely used in water correction, solution decolours, dye desalination is dense
Contracting and biochemical substances purified concentration etc.；Wherein, the rejection of film, water flux, stability etc. can be carried out excellent by composite nanometer filtering film
Further use after change so that on market more than 90% NF membrane application be all composite nanometer filtering film.
Composite nanometer filtering film refer on open support hypoglyph compound one layer the thinnest, fine and close, have special separation function
Different materials；Compared with traditional Integral filter membrane, surface compact layer thickness is thinner for it, have high solute separation rate and water
Transmission rates and the physicalchemical structure that can optimize, it is possible to meet different Selective Separation demands.
The interfacial polymerization mode that in prior art, composite nanometer filtering film mainly uses is prepared, such as Patent No. US4277344
In introduction, first polysulfones is coated in the micropore counterdie formed on polyester non-woven fabric and is immersed in diamidogen or many amine aqueous solutions
In, then remove membrane removal excess surface amine aqueous solution by methods such as wind pouring, roll-ins, then be immersed in the organic nonpolar molten of polynary acyl chlorides
With acyl chlorides generation interface polymerization reaction in liquid, thus form the polyamide ultrathin activity with separation function of densification on surface
Layer, after film forming, fully washing and suitable heat cure processes and can increase film properties.
And composite nanometer filtering film continuous service temperature of the prior art have to be lower than 50 DEG C, if it exceeds this temperature, it will
Cause composite nanometer filtering film quickly to lose normal performance, cause the serious curtailment in service life of film.And food, beverage, pharmacy,
In the industries such as electronics, generally require and produce at relatively high temperatures and act on, such as: biology kills in pharmacy and biological engineering
Microbial inoculum can not be used, and high-temperature-hot-water sterilization can be used；And it is found that high-temperature-hot-water can at Pasteur in 1865
By antibacterial or microorganism killing to a level of security.It is shown in Table 1:
Table 1
| Microorganism | Yeast | Fungus | Antibacterial | Virus |
| Tolerable temperature/time | 80 DEG C/5-10 minute | 80 DEG C/30 minutes | 60-70 DEG C/10 minutes | 60 DEG C/30 minutes |
Visible, Pasteur heat sterilization principle is: heat is conducted to microorganism by hot water, causes the egg in microbial body
White matter deformation of chain and condensation, thus cause microorganism to lose activity.In European and American areas, along with pharmaceuticals industry production standard not
Disconnected raising, disinfection with hot water type water treatment system is the most more and more used, and in Pasteur heat sterilization principle
The temperature that processes of water be substantially all higher than 50 DEG C, therefore use composite nanometer filtering film when processing in water treatment facilities, hold
Being easily caused relatively costly, water treatment facilities are shorter for service life；Therefore, for developing a kind of resistant to elevated temperatures composite nanometer filtering film product
Imperative.
Graphene oxide is the derivant of Graphene, and Graphene is that the unique Two Dimensional Free state existed having now been found that is former
Sub-crystal, is to construct zero dimension fullerene, one-dimensional CNT, the basic structural unit of three-dimensional graphite.It has high conductance, high heat
Lead, peculiar physics, the chemical property such as high rigidity and high intensity, have at electronics, information, the energy, material and biomedicine field
Wide application prospect.But Graphene is owing to powerful Van der Waals force has hydrophobicity and easily reunites, and limits it
Extensively application.Graphene oxide is single or multiple lift graphite oxide that is peeling-off by graphite oxide and that formed, has typical
Quasi-two-dimensional space structure, containing a lot of oxy radicals on its lamella, has higher specific surface energy, good hydrophilic and machinery
Performance, has good dispersion stabilization in water and most of polar organic solvent.Compared with Graphene, graphene oxide has
More excellent performance, it not only has good wettability and surface activity, and can be inserted by little molecule or polymer
Peeling off after Ceng, play very important effect in terms of improving the combination properties such as the calorifics of material, electricity, mechanics, it is concrete
Structure shown in Figure 6.
Although in prior art, having employing graphene oxide to join in NF membrane functional layer, to realize the parent of NF membrane
Aqueous can improve, and overcomes the technical problem of the hydrophilic difference of polysulphones hyperfiltration membrane in prior art；As number of patent application is
201610040730.3 " preparation method of high-hydrophilic polysulphones hyperfiltration membrane ".But prior art joins for Graphene
In NF membrane, its purpose is to improve the hydrophilicity of NF membrane, and for NF membrane resistance to elevated temperatures improvement whether,
Do not make any description and interpretation, and there are no any report yet graphene oxide is used for modified composite nanometer filtering film
After so that the report that NF membrane resistance to elevated temperatures improves.
In consideration of it, this researcher is studied by the technique that graphene oxide carries out composite nanometer filter membrane modifying, it is multiple
The improvement closing NF membrane resistance to elevated temperatures provides a kind of new approaches.
Summary of the invention
In order to solve above-mentioned technical problem present in prior art, the present invention provides a kind of grafted graphene oxide coating
High temperature resistant composite nanometer filtering film and preparation method thereof.
It is achieved particular by techniques below scheme:
A kind of grafted graphene oxide coating high temperature resistant composite nanometer filter membrane preparation method, comprises the following steps:
(1) add graphene oxide in solvent, stir 0.5-2h, add polymer, continue stirring 6-10h, control
Temperature is 60-120 DEG C, and deaeration is cooled to 10-40 DEG C, obtains polymer solution；
(2) polymer solution step (1) prepared uses liquid-solid phase conversion method, using non-woven fabrics as backing material, system
The standby porous polymer supporting layer containing graphene oxide；And by the porous polymer supporting layer employing official containing graphene oxide
Activator activation processing can be rolled into a ball, obtain porous polymer supporting layer；
(3) 0.1-5.0wt% piperazine, 0.001-5.0wt% surfactant and pH adjusting agent are sequentially added in water, stir
Mixing 10-30min complete to dissolving, obtain solution A, pH value is 8-12；0.01-2.0wt% pyromellitic trimethylsilyl chloride is joined organic
In solvent, stirring 10-30min, to dissolving completely, obtains B solution；
(4) porous polymer supporting layer step (2) obtained immerses in solution A, impregnates 1-100s, drains surface water
Pearl, immerses B solution, impregnates 1-200s, after surface volatilization is dry, uses the water of 60-90 DEG C to process 2-20min, denseer by quality
Degree is 0.5-20%, and temperature is the glycerol dipping 5-30min of 15-80 DEG C, then dries,.
Described graphene oxide, its particle diameter is 1-500nm, and concentration in a polymer solution is 0.1-5wt%.
Described solvent is N-N dimethylformamide, N-N dimethyl acetylamide, the one of N-Methyl pyrrolidone or several
Any quality proportioning planted.
Described polymer is in polysulfones, polyether sulfone, polyimides, polypropylene, poly-acetate fiber, halogen polymer
Kind, concentration in a polymer solution is 8-30wt%.
Described functional group's activator is N, N-bicyclic ethyl carbodiimide, N, N-DIC, 1-(3-bis-
Methylaminopropyl) any mass ratio of one or more mixing in-3-ethyl-carbodiimide hydrochloride.
Described functional group's activator solution is to be that 10:1 mix with oxolane according to mass ratio by functional group's activator
After, it is dissolved in DMF solution, wherein functional group's activator mass percent in the solution is 1%-
2%.
Described surfactant be sodium stearate, potassium laurate, dodecylbenzene sodium sulfonate, Disodium sulfosuccinate,
Sodium lauryl sulphate, sodium lauroyl sarcosine, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and
Any mass ratio mixing of one or more in sodium dodecyl aminopropionitrile.
Described pH adjusting agent is sodium hydroxide.
Described organic solvent be hexamethylene, hexane, heptane, octane, Petroleum, Isopar-E, Isopar-G,
Any mass mixing ratio of one or more in Isopar-L and mineral oil.
Described activation processing is that the porous polymer supporting layer containing graphene oxide is immersed in functional group's activator
In solution, soak 1-20min, drain,.
The present invention also provides for the high temperature resistant composite nanometer filtering film of grafted graphene oxide coating prepared by above-mentioned preparation method, bag
Include non-woven fabrics supporting layer, polymeric support layer, stratum disjunctum, between polymeric support layer and stratum disjunctum, be wherein grafted with oxidation stone
Ink ene coatings；It it is polymeric support layer between graphite oxide ene coatings and non-woven fabrics supporting layer.
Graphene oxide particle diameter in the invention is preferably 5-100nm；Graphene oxide is in a polymer solution
Concentration is preferably 0.5-1.5wt%.
Polymer in the invention preferred concentration in a polymer solution is 10-20wt%.
The surfactant in the invention preferred concentration in solution A is 0.01-5wt%, more preferably 0.01-
1wt%.
The pH value of the solution A in the invention is preferably 10.5-11.5.
Drying in the invention uses the hot air dries of 60-100 DEG C and processes.
Functional group's activator solution in the invention is
After 10:1 mixing, it is dissolved in DMF solution, wherein functional group's activator mass percent in the solution
For 1%-2%.
The invention graphene oxide functional group's activation and graft crosslinking principle are as shown in Figure 7.
Compared with prior art, the technique effect of the present invention is embodied in:
After graphene oxide is dissolved in solvent, add polymer formulation polymer solution, then through traditional liquid-solid
Phase inversion preparation is containing graphene oxide porous polymer supporting layer, in conjunction with the activation processing of functional group's activator so that
It is grafted into one layer of graphite oxide ene coatings between the stratum disjunctum and polymeric support layer of composite nanometer filtering film, and integrating step (3),
A, B solution in step (4) soak modification so that graphite oxide ene coatings can enter with polymeric support layer, stratum disjunctum
Row is mutually chemically bonded, and improves the stability of composite nanometer filtering film, improves the resistance to elevated temperatures of composite nanometer filtering film.
The researcher of the invention is by prepared by the technical scheme that number of patent application is 201610040730.3 being combined
NF membrane diaphragm as a comparison case, with the embodiment 1 of the invention, embodiment 2, the composite nanometer filtering film of embodiment 3 preparation, will
Its diaphragm monitor station test, operation pressure be 150psi, former water be 2000ppm MgSO4Aqueous solution, solution temperature are from 25
DEG C gradually rise to about 85 DEG C, pH value be 6.5-7.5 test condition under, test diaphragm run different time water flux and
Removal efficiency, its result is as shown in table 2:
Table 2
The researcher of the invention is by prepared by the technical scheme that number of patent application is 201610040730.3 being combined
NF membrane diaphragm as a comparison case, with the embodiment 1 of the invention, embodiment 2, the composite nanometer filtering film of embodiment 3 preparation, will
Its diaphragm monitor station test, operation pressure be 150psi, former water be 2000ppm MgSO4Aqueous solution, solution temperature keep
About 70 DEG C, pH value be 6.5-7.5 test condition under, long-play, the water flux of record and removal efficiency, result is as follows
Shown in table 3:
Table 3
Visible, the resistance to elevated temperatures of the composite nanometer filtering film of the invention is more excellent, under identical testing conditions, and diaphragm warp
Crossing the operation from low temperature to high temperature, the composite nanometer filter membrane flux of the present invention is less compared with comparative example change, and the stability of salt rejection rate
Being significantly better than conventional composite nanometer filtering film, hot conditions runs down display, the composite nanometer filtering film of the present invention either flux
Or the stability of salt rejection rate is the most excellent.
Accompanying drawing explanation
Fig. 1 is the grafted graphene oxide coating high temperature resistant composite nanometer filtering film hierarchical structure of the present invention.
1-stratum disjunctum 2-graphite oxide ene coatings 3-polymeric support layer 4-non-woven fabrics supporting layer.
Fig. 2 is the diaphragm flux from low-temperature-rise to high temperature and time chart.
Fig. 3 is the diaphragm salt rejection rate from low-temperature-rise to high temperature and time chart.
Fig. 4 is flux and the time chart of diaphragm long-play test under high temperature.
Fig. 5 is salt rejection rate and the time chart of diaphragm long-play test under high temperature.
Fig. 6 is graphene oxide structure.
Fig. 7 is activation and the graft crosslinking schematic diagram of graphene oxide functional group.
Detailed description of the invention
With specific embodiment, technical scheme is further limited below in conjunction with the accompanying drawings, but requirement
The scope of protection is not only limited to description.
The invention is in the practice of industrialized production product, and it can enter according to mode of operation in detail below
OK: a kind of grafted graphene oxide coating high temperature resistant composite nanometer filter membrane preparation method, comprise the following steps:
(1) add graphene oxide in solvent, stir 0.5-2h, add polymer, continue stirring 6-10h, control
Temperature is 60-120 DEG C, and deaeration is cooled to 10-40 DEG C, obtains polymer solution；
(2) polymer solution step (1) prepared uses liquid-solid phase conversion method, using non-woven fabrics as backing material, system
The standby porous polymer supporting layer containing graphene oxide；And by the porous polymer supporting layer employing official containing graphene oxide
Activator activation processing can be rolled into a ball, obtain porous polymer supporting layer；
(3) 0.1-5.0wt% piperazine, 0.001-5.0wt% surfactant and pH adjusting agent are sequentially added in water, stir
Mixing 10-30min complete to dissolving, obtain solution A, pH value is 8-12；0.01-2.0wt% pyromellitic trimethylsilyl chloride is joined organic
In solvent, stirring 10-30min, to dissolving completely, obtains B solution；
(4) porous polymer supporting layer step (2) obtained immerses in solution A, impregnates 1-100s, drains surface water
Pearl, immerses B solution, impregnates 1-200s, after surface volatilization is dry, uses the water of 60-90 DEG C to process 2-20min, denseer by quality
Degree is 0.5-20%, and temperature is the glycerol dipping 5-30min of 15-80 DEG C, then dries,.
In certain embodiments, graphene oxide, particle diameter is 1-500nm, and concentration in a polymer solution is 0.1-
5wt%.
In certain embodiments, in solvent N-N dimethylformamide, N-N dimethyl acetylamide, N-Methyl pyrrolidone
Any quality proportioning of one or more.
In certain embodiments, polymer be polysulfones, polyether sulfone, polyimides, polypropylene, poly-acetate fiber, halogenation gather
One in compound, concentration in a polymer solution is 8-30wt%.
In certain embodiments, functional group's activator is N, N-bicyclic ethyl carbodiimide, N, N-diisopropyl carbon two Asia
Any mass ratio of one or more mixing in amine, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride.
In certain embodiments, functional group's activator solution is to be according to mass ratio with oxolane by functional group's activator
After 10:1 mixing, it is dissolved in DMF solution, wherein functional group's activator mass percent in the solution
For 1%-2%.
In certain embodiments, surfactant is sodium stearate, potassium laurate, dodecylbenzene sodium sulfonate, succinic acid
Ester sodium sulfonate, sodium lauryl sulphate, sodium lauroyl sarcosine, Dodecyl trimethyl ammonium chloride, dodecyl dimethyl benzyl
Any mass ratio mixing of one or more in ammonium chloride and sodium dodecyl aminopropionitrile.
In certain embodiments, pH adjusting agent is sodium hydroxide.
In certain embodiments, organic solvent be hexamethylene, hexane, heptane, octane, Petroleum, Isopar-E,
Any mass mixing ratio of one or more in Isopar-G, Isopar-L and mineral oil.
In certain embodiments, activation processing is that the porous polymer supporting layer containing graphene oxide is immersed in sense
In group's activator solution, soak 1-20min, drain,.
This is high temperature resistant composite nanometer filtering film, including non-woven fabrics supporting layer, polymeric support layer, stratum disjunctum, wherein at polymer
Graphite oxide ene coatings it is grafted with between supporting layer and stratum disjunctum；For being polymerized between graphite oxide ene coatings with non-woven fabrics supporting layer
Thing supporting layer.
In certain embodiments, graphene oxide particle diameter is preferably 5-100nm；Graphene oxide is in a polymer solution
Concentration is preferably 0.5-1.5wt%.
In certain embodiments, polymer preferred concentration in a polymer solution is 10-20wt%.
In certain embodiments, surfactant preferred concentration in solution A is 0.01-5wt%, more preferably
0.01-1wt%.
In certain embodiments, the pH value of solution A is preferably 10.5-11.5.
In certain embodiments, drying uses the hot air dries process of 60-100 DEG C.
In certain embodiments, functional group's activator solution is to be according to mass ratio with oxolane by functional group's activator
After 10:1 mixing, it is dissolved in DMF solution, wherein functional group's activator mass percent in the solution
It is 1%～2%.
In certain embodiments, the activation of graphene oxide functional group and graft crosslinking principle are as shown in Figure 7.
Embodiment 1
Take DMF, by graphene oxide dispersed with stirring that particle diameter is 15nm wherein, in dispersion liquid
Solid content is less than 20%；Add polysulfones, stir；Concrete mode of operation is to add graphene oxide into N, N-dimethyl
In Methanamide, stirring 1h, add polysulfones, continue stirring 7h, controlling temperature is 110 DEG C, and deaeration is cooled to 30 DEG C, is polymerized
Thing solution；Wherein graphene oxide mass concentration in a polymer solution is 0.5wt%, polysulfones in a polymer solution dense
Degree is 8-30wt%；
The polymer solution step (1) prepared uses liquid-solid phase conversion method, using non-woven fabrics as backing material, according to
Traditional preparation method is prepared the porous polymer supporting layer containing graphene oxide；
By N, N-bicyclic ethyl carbodiimide (DCC), that oxolane (THF) solves homogeneously in DMF is molten
In liquid, wherein N, N-bicyclic ethyl carbodiimide (DCC), the mass ratio of oxolane (THF) are 10:1, N, N-bicyclo-ethyl carbon
Diimine (DCC) mass concentration accounting in the solution is 1%, it is thus achieved that functional group's activator solution；
Porous polymer supporting layer containing graphene oxide is immersed in functional group's activator solution and soak 5min, drip
Dry, it is thus achieved that the composite nanometer filtering film after functional group's activation；
2wt% piperazine, 3wt% Disodium sulfosuccinate and pH adjusting agent being sequentially added in water, stirring 20min is to dissolving
Completely, obtaining solution A, pH value is 11；1.0wt% pyromellitic trimethylsilyl chloride is joined hexamethylene, hexane, heptane according to any quality
In mixture than mixing, stirring 20min, to dissolving completely, obtains B solution；
Composite nanometer filtering film after functional group being activated immerses in solution A, impregnates 90s, drains surface water drops, immerses B solution,
Dipping 100s, after surface volatilization is dry, uses the water of 80 DEG C to process 10min, then is 10% by mass concentration, and temperature is 70 DEG C
Glycerol dipping 10min, then dry, the temperature of drying is 70 DEG C,.
Embodiment 2
Take DMF, by graphene oxide dispersed with stirring that particle diameter is 50nm wherein, in dispersion liquid
Solid content is less than 20%；Add polysulfones, stir；Concrete mode of operation is to add graphene oxide into N, N-dimethyl
In Methanamide, stirring 2h, add polysulfones, continue stirring 10h, controlling temperature is 120 DEG C, and deaeration is cooled to 40 DEG C, is polymerized
Thing solution；Wherein graphene oxide mass concentration in a polymer solution is 1wt%, polysulfones concentration in a polymer solution
For 30wt%；
The polymer solution step (1) prepared uses liquid-solid phase conversion method, using non-woven fabrics as backing material, according to
Traditional preparation method is prepared the porous polymer supporting layer containing graphene oxide；
By N, N-bicyclic ethyl carbodiimide (DCC), that oxolane (THF) solves homogeneously in DMF is molten
In liquid, wherein N, N-bicyclic ethyl carbodiimide (DCC), the mass ratio of oxolane (THF) are 10:1, N, N-bicyclo-ethyl carbon
Diimine (DCC) mass concentration accounting in the solution is 1%, it is thus achieved that functional group's activator solution；
Porous polymer supporting layer containing graphene oxide is immersed in functional group's activator solution and soak 5min, drip
Dry, it is thus achieved that the composite nanometer filtering film after functional group's activation；
5.0wt% piperazine, 5.0wt% Disodium sulfosuccinate are mixed according to any mass ratio with dodecylbenzene sodium sulfonate
Mixture and pH adjusting agent after conjunction are sequentially added in water, and stirring 30min, to dissolving completely, obtains solution A, and pH value is 12；Will
2.0wt% pyromellitic trimethylsilyl chloride joins in hexamethylene, the ethyl cyclohexane mixture according to any mass ratio, stirs 30min
To dissolving completely, obtain B solution；
Composite nanometer filtering film after functional group being activated immerses in solution A, impregnates 100s, drains surface water drops, immerses B molten
Liquid, impregnates 200s, after surface volatilization is dry, uses the water of 90 DEG C to process 20min, then is 20% by mass concentration, and temperature is 80
DEG C glycerol dipping 30min, then dry, the temperature of drying is 60 DEG C,.
Embodiment 3
Take DMF, by graphene oxide dispersed with stirring that particle diameter is 5nm wherein, consolidating in dispersion liquid
Content is less than 20%；Add polysulfones, stir；Concrete mode of operation is to add graphene oxide into N, N-dimethyl methyl
In amide, stirring 0.5h, add polysulfones, continue stirring 6h, controlling temperature is 60 DEG C, and deaeration is cooled to 10 DEG C, obtains polymer
Solution；Wherein graphene oxide mass concentration in a polymer solution is 0.1wt%, polysulfones concentration in a polymer solution
For 8wt%；
The polymer solution step (1) prepared uses liquid-solid phase conversion method, using non-woven fabrics as backing material, according to
Traditional preparation method is prepared the porous polymer supporting layer containing graphene oxide；
By N, N-bicyclic ethyl carbodiimide (DCC), that oxolane (THF) solves homogeneously in DMF is molten
In liquid, wherein N, N-bicyclic ethyl carbodiimide (DCC), the mass ratio of oxolane (THF) are 10:1, N, N-bicyclo-ethyl carbon
Diimine (DCC) mass concentration accounting in the solution is 2%, it is thus achieved that functional group's activator solution；
Porous polymer supporting layer containing graphene oxide is immersed in functional group's activator solution and soak 5min, drip
Dry, it is thus achieved that the composite nanometer filtering film after functional group's activation；
0.1wt% piperazine, 0.001wt% dodecylbenzene sodium sulfonate and pH adjusting agent are sequentially added in water, stirring
10min, to dissolving completely, obtains solution A, and pH value is 8；0.01wt% pyromellitic trimethylsilyl chloride is joined in ethyl cyclohexane, stirring
10min, to dissolving completely, obtains B solution；
Composite nanometer filtering film after functional group being activated immerses in solution A, impregnates 1s, drains surface water drops, immerses B solution,
Dipping 1s, after surface volatilization is dry, uses the water process 2min of 60 DEG C, then is 0.5% by mass concentration, and temperature is 15 DEG C sweet
Oil-impregnated 5min, then dry, drying is the hot air dries of employing 80 DEG C,.
Above example is only limitted to make technical scheme further explanation and explanation, not to the present invention
Technical scheme further limited, be not the poor of all of exercisable technical scheme to the invention simultaneously
To the greatest extent formula is enumerated, and therefore, the protection domain for the invention should be as the criterion with above-mentioned endpoint value, any does on this basis
Go out does not has prominent essential characteristics and the improvement of non-significant progress, belongs to the protection category of the present invention.
Claims (11)
1. a grafted graphene oxide coating high temperature resistant composite nanometer filter membrane preparation method, it is characterised in that comprise the following steps:
(1) add graphene oxide in solvent, stir 0.5-2h, add polymer, continue stirring 6-10h, control temperature
For 60-120 DEG C, deaeration, it is cooled to 10-40 DEG C, obtains polymer solution；
(2) polymer solution step (1) prepared uses liquid-solid phase conversion method, contains using non-woven fabrics as backing material, preparation
There is the porous polymer supporting layer of graphene oxide；And the porous polymer supporting layer containing graphene oxide is used functional group
Activator solution activation processing, obtains porous polymer supporting layer；
(3) 0.1-5.0wt% piperazine, 0.001-5.0wt% surfactant and pH adjusting agent are sequentially added in water, stirring
10-30min, to dissolving completely, obtains solution A, and pH value is 8-12；0.01-2.0wt% pyromellitic trimethylsilyl chloride is joined organic molten
In agent, stirring 10-30min, to dissolving completely, obtains B solution；
(4) porous polymer supporting layer step (2) obtained immerses in solution A, impregnates 1-100s, drains surface water drops, leaching
Enter B solution, impregnate 1-200s, after surface volatilization is dry, uses the water of 60-90 DEG C to process 2-20min, then by mass concentration be
0.5-20%, temperature is the glycerol dipping 5-30min of 15-80 DEG C, then dries,.
2. preparation method as claimed in claim 1, it is characterised in that described graphene oxide, its particle diameter is 1-500nm,
Concentration in a polymer solution is 0.1-5wt%.
3. preparation method as claimed in claim 1, it is characterised in that the solvent in described step (1) is N-N dimethyl formyl
Any quality proportioning of one or more in amine, N-N dimethyl acetylamide, N-Methyl pyrrolidone.
4. preparation method as claimed in claim 1, it is characterised in that described polymer is polysulfones, polyether sulfone, polyamides Asia
One in amine, polypropylene, poly-acetate fiber, halogen polymer, concentration in a polymer solution is 8-30wt%.
5. preparation method as claimed in claim 1, it is characterised in that described functional group's activator is N, N-bicyclo-ethyl carbon
Diimine, N, one in N-DIC, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride or
Several any mass ratio mixing.
6. preparation method as claimed in claim 1, it is characterised in that described functional group's activator solution is functional group to be lived
Agent is after 10:1 mixes with oxolane according to mass ratio, is dissolved in DMF solution, wherein functional group
Activator mass percent in the solution is 1%-2%.
7. preparation method as claimed in claim 1, it is characterised in that described surfactant is sodium stearate, lauric acid
Potassium, dodecylbenzene sodium sulfonate, Disodium sulfosuccinate, sodium lauryl sulphate, sodium lauroyl sarcosine, dodecyl front three
Any quality of one or more in ammonium chloride, dodecyl dimethyl benzyl ammonium chloride and sodium dodecyl aminopropionitrile
Than mixing.
8. preparation method as claimed in claim 1, it is characterised in that described pH adjusting agent is sodium hydroxide.
9. preparation method as claimed in claim 1, it is characterised in that described organic solvent be hexamethylene, hexane, heptane,
Any mass mixing ratio of one or more in octane, Petroleum, Isopar-E, Isopar-G, Isopar-L and mineral oil.
10. preparation method as claimed in claim 1, it is characterised in that described activation processing is by containing graphene oxide
Porous polymer supporting layer be immersed in functional group's activator solution, soak 1-20min, drain,.
High temperature resistant being combined of grafted graphene oxide coating prepared by 11. preparation methoies as described in any one of claim 1-10 is received
Filter membrane, it is characterised in that include non-woven fabrics supporting layer, polymeric support layer, stratum disjunctum, wherein polymeric support layer with separate
Graphite oxide ene coatings it is grafted with between Ceng；It it is polymeric support layer between graphite oxide ene coatings and non-woven fabrics supporting layer.
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