CN102908914B - Composite separating membrane with alloy ultrafiltration layer and preparation method of composite separating membrane - Google Patents
Composite separating membrane with alloy ultrafiltration layer and preparation method of composite separating membrane Download PDFInfo
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- CN102908914B CN102908914B CN201210413362.4A CN201210413362A CN102908914B CN 102908914 B CN102908914 B CN 102908914B CN 201210413362 A CN201210413362 A CN 201210413362A CN 102908914 B CN102908914 B CN 102908914B
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- 238000000108 ultra-filtration Methods 0.000 title claims abstract description 87
- 239000000956 alloy Substances 0.000 title claims abstract description 72
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 72
- 239000012528 membrane Substances 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 38
- 229920000642 polymer Polymers 0.000 claims abstract description 38
- 239000002904 solvent Substances 0.000 claims abstract description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 11
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 10
- 239000004952 Polyamide Substances 0.000 claims abstract description 6
- 229920002647 polyamide Polymers 0.000 claims abstract description 6
- 239000011780 sodium chloride Substances 0.000 claims abstract description 6
- 230000001939 inductive effect Effects 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 32
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 32
- 229920002492 poly(sulfone) Polymers 0.000 claims description 25
- 239000004695 Polyether sulfone Substances 0.000 claims description 24
- 229920006393 polyether sulfone Polymers 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 18
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- 239000004760 aramid Substances 0.000 claims description 12
- 229920003235 aromatic polyamide Polymers 0.000 claims description 12
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229920001747 Cellulose diacetate Polymers 0.000 claims description 9
- BAZVSMNPJJMILC-UHFFFAOYSA-N triadimenol Chemical compound C1=NC=NN1C(C(O)C(C)(C)C)OC1=CC=C(Cl)C=C1 BAZVSMNPJJMILC-UHFFFAOYSA-N 0.000 claims description 9
- 238000004090 dissolution Methods 0.000 claims description 8
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 7
- 229920000491 Polyphenylsulfone Polymers 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 7
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- ZBZGGZGVFCIXDE-UHFFFAOYSA-N 5-amino-2-(4-aminophenyl)benzenesulfonic acid Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1S(O)(=O)=O ZBZGGZGVFCIXDE-UHFFFAOYSA-N 0.000 claims description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 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 description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 229910052799 carbon Chemical group 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229920006239 diacetate fiber Polymers 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 125000000962 organic group Chemical group 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000003361 porogen Substances 0.000 claims description 2
- 239000002352 surface water Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 229920006304 triacetate fiber Polymers 0.000 claims description 2
- 238000001223 reverse osmosis Methods 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000010612 desalination reaction Methods 0.000 abstract description 3
- 238000007598 dipping method Methods 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000001728 nano-filtration Methods 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 31
- 229910021641 deionized water Inorganic materials 0.000 description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 239000000463 material Substances 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- 230000004907 flux Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 6
- 238000010406 interfacial reaction Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 239000013557 residual solvent Substances 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 4
- 229960002668 sodium chloride Drugs 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- -1 polychloroethylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
Abstract
The invention provides a composite separating membrane with an alloy ultrafiltration layer. The composite separating membrane comprises non-woven fabric, an ultrafiltration supporting layer and a polyamide layer, wherein the ultrafiltration supporting layer is an alloy ultrafiltration supporting layer, which includes more than two polymers and at least one reactive monomer; and the polyamide layer is formed by the contact between the solution with amine monomer and the solution with acyl chloride monomer on the alloy ultrafiltration supporting layer. A preparation method of the composite separating membrane comprises the following steps of: preparing polymer solution; separating to remove the solvent by a nonsolvent inductive phase; dipping in a solution A; and then dipping in a solution B. According to the composite separating membrane, the ultrafiltration supporting layer of a composite separation membrane pair is high in peeling strength and high in surface smoothness; the polyamide layer is high in resistance to scratch and good in desalination effect; and the composite separating membrane has not less than 0.8N of peeling resistance respect to a non-woven fabric layer, and has not less than 99.5% of desalination rate respect to 4000ppm of NaCl solution under 225Psi. The preparation method provided by the invention can be used for preparing high-performance reverse osmosis membranes, nanofiltration membranes, and the ultrafiltration membranes with low molecular cut off.
Description
Technical field
The present invention relates to and a kind of there is composite separating film of alloy ultrafiltration layer and preparation method thereof, belong to water treatment field.
Background technology
In the evolution of membrane separation technique, the research starting of organic separation membrane early, development is fast, be widely used, good, the selective height of organic film pliability, preparation process is simple, technics comparing is ripe, and low price, but its poor heat stability, not acid and alkali resistance and organic solvent, use the easy life-span short under adverse circumstances, and easily block, not easy cleaning and Reusability.Inoranic membrane, compared with organic film, has heat endurance, chemical stability and mechanical stability good, and not aging, life-span length, easy cleaning, be convenient to control the advantage such as pore size and distribution.But inoranic membrane also has the weak points such as more crisp, processing difficulties.Organic-inorganic composite diffusion barrier is exactly the advantages by organic film and inoranic membrane, makes it the stability both with inoranic membrane, has again the surface characteristic that organo-functional group is given.One of Synthesis and applications main development direction having become field of membrane science of composite separating film.Composite separating film is formed by two or more material or structure composite, has the film of separation function.Along with the development of science and technology, current existing polymer can not meet the requirement of separation membrane material.More new synthetic material and material modifiedly to occur, is causing the attention of people by the blended work improving membrane material and membrane structure and performance of macromolecular material.Alloy ultrafiltration membrane is that a kind of aperture is less, has higher water flux and the milipore filter of rejection, and conventional blending technology, with phase inversion masking.At present, the composite separating film of organic load, such as on polysulfones microporous barrier coated with polyamide film, due to heat resistance and the corrosion-resistant of organic load, intensity is not high yet.Reverse osmosis membrane is different with the preparation method of milipore filter with the preparation method of NF membrane, and structure is also different, the more difficult advantage possessing alloy ultrafiltration membrane.
China ZL200810062570.8 discloses a kind of preparation method of hydrophilic polyvinyl chloride alloy ultrafiltration membrane, the amphipathic graft copolymer of polyvinyl chloride has been synthesized, as clear water modifier and the polychloroethylene blended polyvinyl chloride alloy ultrafiltration membrane having been prepared structure-controllable, hydrophily, antipollution, large flux, high rejection by solution phase inversion by atom transfer radical polymerization method.The program is applicable to the preparation of polyvinyl chloride alloy ultrafiltration membrane, is but unsuitable for preparing other diffusion barriers with alloy ultrafiltration layer, as reverse osmosis membrane and NF membrane.
The ultrafiltration supporting layer of alloy ultrafiltration membrane of the prior art is to the antistripping ability of nonwoven layer, and the anti-scuffing function of aramid layer is not very desirable.
Summary of the invention
The invention provides and a kind of there is composite separating film of alloy ultrafiltration layer and preparation method thereof, solve the problem that the anti-scuffing function of the antistripping ability of the nonwoven layer of composite separating film in prior art and aramid layer is undesirable.
Technical scheme of the present invention is as follows:
There is a composite separating film for alloy ultrafiltration supporting layer, comprise nonwoven layer, ultrafiltration supporting layer and aramid layer; Described ultrafiltration supporting layer is alloy ultrafiltration supporting layer, and containing two kinds and above polymer and reactive monomer, and reactive monomer is identical with any one or several in synthesizing polyamides layer monomer used; Alloy ultrafiltration supporting layer is induced to be separated by the solution coating carried out in nonwoven surface and the non-solvent carried out in non-solvent and is prepared from; Described aramid layer to be contacted with the solution containing acyl chlorides monomer by the solution containing amine monomers and is formed on alloy ultrafiltration supporting layer.
The above-mentioned preparation method with the composite separating film of alloy ultrafiltration supporting layer, is characterized in that: mainly comprise the following steps:
(1) prepared polymer solution: pore former and reactive monomer are placed in solvent in proportion, stir, then two kinds and above polymer raw material are placed in solvent in proportion, it is 30 ~ 90 ° of C that rapid stirring also heats up, dissolve 1 ~ 24h, gained solution left standstill vacuum defoamation 4 ~ 48h, deaeration vacuum-0.07Mpa, obtains polymer solution; In solution, the total content of polymer is 5 ~ 30wt%, and reactive monomer content is 0.1 ~ 20wt%, and porogen content is 0.5 ~ 20wt%;
(2) induce with non-solvent the removal solvent that is separated: be coated on non-woven fabrics by resulting polymers dissolution homogeneity in step (1), be placed in non-solvent, temperature is 10 ~ 50 ° of C, induction forms alloy ultrafiltration supporting layer after being separated and removing solvent;
(3) be immersed in solution A: alloy ultrafiltration supporting layer described in step (2) is soaked in 1 ~ 300s in the solution A be mixed with by the m-phenylene diamine (MPD) of 0.1 ~ 5wt% and/or piperazine monomer and water, take out after leaving standstill certain hour, drain surface water drops;
(4) be immersed in B solution: the alloy ultrafiltration membrane processed through step (3) is contacted 1 ~ 100s with the B solution of the pyromellitic trimethylsilyl chloride monomer containing 0.01 ~ 5wt%, form aramid layer, after air-dry surface solvent, obtain composite separating film; Wherein, B solution solvent for use is any one or several in cyclohexane, heptane, octane, ISOPAR-E, ISOPAR-G and ISOPAR-L.
In polymer raw material in described step (1), wherein one is polysulfones, also comprises any one or several in polyether sulfone, PPSU, sulfonated polyether sulfone, polyvinyl chloride, polyimides, Triafol T, cellulose diacetate and Kynoar in addition;
When polymer raw material is made up of polysulfones and polyether sulfone, wherein the weight ratio of polyether sulfone in alloy-layer is 0.1 ~ 20wt%, is preferably 0.5 ~ 5wt%;
When polymer raw material is made up of polysulfones and PPSU, wherein the weight ratio of PPSU in alloy-layer is 0.01 ~ 10wt%, is preferably 0.1 ~ 5wt%;
When polymer raw material is made up of polysulfones and sulfonated polyether sulfone, wherein the weight ratio of sulfonated polyether sulfone in alloy-layer is 0.1 ~ 10wt%, is preferably 0.5 ~ 5wt%;
When polymer raw material is made up of polysulfones, polyether sulfone and sulfonated polyether sulfone, wherein the weight ratio of polyether sulfone in alloy-layer is 0.1 ~ 15wt%, and be preferably 0.1 ~ 5wt%, the weight ratio of sulfonated polyether sulfone in alloy-layer is 0.1 ~ 5wt%;
When polymer raw material is made up of polysulfones and Triafol T, wherein the weight ratio of triacetate fiber in alloy-layer is 0.1 ~ 15wt%, is preferably 0.1 ~ 5wt%;
When alloy ultrafiltration supporting layer is made up of polysulfones and polyether sulfone, wherein the weight ratio of polyether sulfone in alloy-layer is 0.1 ~ 20wt%, is preferably 0.5 ~ 5wt%;
When polymer raw material is made up of polysulfones and cellulose diacetate, wherein the weight ratio of cellulose diacetate in alloy-layer is 0.1 ~ 20wt%, is preferably 0.1 ~ 5wt%;
When polymer raw material is made up of polysulfones, Triafol T and cellulose diacetate, wherein the weight ratio of Triafol T in alloy-layer is 0.1 ~ 10wt%, be preferably 0.5 ~ 5wt%, the weight ratio of diacetate fiber in alloy-layer is 0.1 ~ 20wt%, is preferably 0.1 ~ 5wt%.
Reactive monomer in described step (1) is amine monomers, acyl chloride monomer and containing any one or several in-NCO monomer.
The concentration of described amine monomers is 0.01 ~ 10wt%, be preferably 0.01 ~ 5wt%, refer to ethylenediamine, triethylamine, hexamethylene diamine, p-phenylenediamine (PPD), o-phenylenediamine, m-phenylene diamine (MPD), piperazine, O-phthalic amine, p dimethylamine, m-xylene diamine, 2, any one or several in 2 '-benzidine sulfonic acid; Be preferably m-phenylene diamine (MPD), piperazine, p-phenylenediamine (PPD) and 2, any one or several in 2 '-benzidine sulfonic acid.
The concentration of described acyl chloride monomer is 0.01 ~ 10wt%, is preferably 0.01 ~ 2wt%, refers to any one or several in acyl chlorides of pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride and biphenyl four.
The molecular configuration of the described monomer containing-NCO functional group is characterized as NCO-R-NCO, and wherein R is organic group, and carbon containing number is 2 ~ 18; Its concentration in alloy ultrafiltration supporting layer is 0.01 ~ 10wt%, is preferably 0.01 ~ 2wt%.
Solvent in described step (1) refers to any one or several in DMF, DMA, N, N-dimethyl pyrrolidone, acetone and methyl-sulfoxide.
Pore former in described step (1) refers to any one or several in sodium chloride, lithium chloride, PVP, polyethylene glycol and glycol monoethyl ether.
In described step (2) for inducing the non-solvent be separated to be any one or several in water, ethanol, isopropyl alcohol, the tert-butyl alcohol and glycerine.
Beneficial effect of the present invention: compared with the ultrafiltration supporting layer that common composite separating film is used, the ultrafiltration supporting layer of composite separating film of the present invention is alloy ultrafiltration layer, it is mixed in proportion by two kinds and above polymer and forms, and alloyed polymers effectively can promote it to the antistripping ability of nonwoven layer and the anti-scuffing function promoting aramid layer; The reactive monomer contained in alloy ultrafiltration supporting layer can make the adhesion of aramid layer and ultrafiltration layer stronger, improves membrane material to the removal efficiency of sodium chloride while improving anti-scuffing function.Composite separating film of the present invention has higher peel strength and surface smoothness to ultrafiltration supporting layer, and aramid layer has better anti-scuffing function and desalting ability; 0.8N is not less than to the peel strength of nonwoven layer; Under 225Psi, 99.5% is not less than to the salt rejection rate of 4000ppmNaCl solution; Preparation method of the present invention can be used for the milipore filter of the excellent reverse osmosis membrane of processability, NF membrane and low catching molecular.
Accompanying drawing explanation
Fig. 1 is the resistance to marring result of the test figure of the embodiment of the present invention 1 gained composite separating film;
Fig. 2 is the resistance to marring result of the test figure of the embodiment of the present invention 2 gained composite separating film;
Fig. 3 is the resistance to marring result of the test figure of comparative film gained composite separating film.
Detailed description of the invention
In order to deepen to understand the present invention, below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, and this embodiment only for explaining the present invention, does not form limiting the scope of the present invention.
Embodiment 1
(1) prepared polymer solution: 20g glycol monoethyl ether and 20g m-phenylene diamine (MPD) are scattered in 780gN, in N-dimethylacetylamide, 30min is stirred at 1600 rpm with mechanical agitator, thereafter 120g polysulfones and 60g PPSU are dispensed into wherein, and intensification is 80 DEG C, stirring and dissolving under 1400rpm rotating speed, dissolution time 12h, deaeration vacuum-80KPa.Thing to be polymerized dissolves completely, gained solution is placed in vacuum drying oven standing and defoaming, inclined heated plate 10h.
(2) to be separated removal solvent with non-solvent induction: by the alloy ultrafiltration supporting layer of preparation in step (1), with deaeration, solution scraper even application is on non-woven fabrics base material completely, and the deionized water being placed in 20 DEG C is carried out process and obtained alloy ultrafiltration membrane; Gained alloy ultrafiltration membrane deionized water continues rinsing to remove residual solvent, and preserves in deionized water.
(3) be immersed in solution A: 45g m-phenylene diamine (MPD) and 2g NaOH are dissolved in 953g deionized water, stirring and dissolving obtains solution A completely.The alloy ultrafiltration membrane of preparation in step (2) is soaked 30s in solution A, and taking-up drains.
(4) be immersed in B solution: be dissolved in cyclohexane by 2.0g pyromellitic trimethylsilyl chloride, stirring and dissolving obtains B solution.The alloy ultrafiltration membrane having soaked solution A in step (3) is placed in B solution and carries out interfacial reaction, reaction time 20s, preserve in deionized water after taking out the residual cyclohexane of air-dry face.
Embodiment 2
(1) prepared polymer solution: 20g sodium chloride and 20g m-phenylene diamine (MPD) are scattered in 780g N, in dinethylformamide, 30min is stirred at 1600 rpm with mechanical agitator, thereafter 120g polysulfones and 60g cellulose diacetate are dispensed into wherein, and intensification is 90 DEG C, stirring and dissolving under 1400rpm rotating speed, dissolution time 14h, deaeration vacuum-80KPa.Thing to be polymerized dissolves completely, gained solution is placed in vacuum drying oven standing and defoaming, inclined heated plate 4h.
(2) to be separated removal solvent with non-solvent induction: by the alloy ultrafiltration supporting layer of preparation in step (1), with deaeration, solution scraper even application is on non-woven fabrics base material completely, and the deionized water being placed in 20 DEG C is carried out process and obtained alloy ultrafiltration membrane; Gained alloy ultrafiltration membrane deionized water continues rinsing to remove residual solvent, and preserves in deionized water.
(3) be immersed in solution A: 45g m-phenylene diamine (MPD) and 2g NaOH are dissolved in 953g deionized water, stirring and dissolving obtains solution A completely.The alloy ultrafiltration membrane of preparation in step (2) is soaked 60s in solution A, and taking-up drains.
(4) be immersed in B solution: be dissolved in ISOPAR-G by 2.0g pyromellitic trimethylsilyl chloride, stirring and dissolving obtains B solution.The alloy ultrafiltration membrane having soaked solution A in step (3) is placed in B solution and carries out interfacial reaction, reaction time 40s, preserve in deionized water after taking out the residual cyclohexane of air-dry face.
Embodiment 3
(1) prepared polymer solution: 20g lithium chloride and 20g m-phenylene diamine (MPD) are scattered in 780g N, in N-dimethyl pyrrolidone, 30min is stirred at 1600 rpm with mechanical agitator, thereafter 120g polysulfones and 60g polyether sulfone are dispensed into wherein, and intensification is 60 DEG C, stirring and dissolving under 1400rpm rotating speed, dissolution time 18h, deaeration vacuum-80KPa.Thing to be polymerized dissolves completely, gained solution is placed in vacuum drying oven standing and defoaming, inclined heated plate 20h.
(2) to be separated removal solvent with non-solvent induction: by the alloy ultrafiltration supporting layer of preparation in step (1), with deaeration, solution scraper even application is on non-woven fabrics base material completely, and the deionized water being placed in 10 DEG C is carried out process and obtained alloy ultrafiltration membrane; Gained alloy ultrafiltration membrane deionized water continues rinsing to remove residual solvent, and preserves in deionized water.
(3) be immersed in solution A: 45g m-phenylene diamine (MPD) and 2g NaOH are dissolved in 953g deionized water, stirring and dissolving obtains solution A completely.The alloy ultrafiltration membrane of preparation in step (2) is soaked 100s in solution A, and taking-up drains.
(4) be immersed in B solution: be dissolved in ISOPAR-E by 2.0g pyromellitic trimethylsilyl chloride, stirring and dissolving obtains B solution.The alloy ultrafiltration membrane having soaked solution A in step (3) is placed in B solution and carries out interfacial reaction, reaction time 100s, preserve in deionized water after taking out the residual cyclohexane of air-dry face.
Embodiment 4
(1) prepared polymer solution: 20g PVP and 20g m-phenylene diamine (MPD) are scattered in 780g acetone, 30min is stirred at 1600 rpm with mechanical agitator, thereafter 120g polysulfones and 60g Triafol T are dispensed into wherein, and intensification is 50 DEG C, stirring and dissolving under 1400rpm rotating speed, dissolution time 20h, deaeration vacuum-80KPa.Thing to be polymerized dissolves completely, gained solution is placed in vacuum drying oven standing and defoaming, inclined heated plate 30h.
(2) to be separated removal solvent with non-solvent induction: by the alloy ultrafiltration supporting layer of preparation in step (1), with deaeration, solution scraper even application is on non-woven fabrics base material completely, and the deionized water being placed in 30 DEG C is carried out process and obtained alloy ultrafiltration membrane; Gained alloy ultrafiltration membrane deionized water continues rinsing to remove residual solvent, and preserves in deionized water.
(3) be immersed in solution A: 45g piperazine and 2g NaOH are dissolved in 953g deionized water, stirring and dissolving obtains solution A completely.The alloy ultrafiltration membrane of preparation in step (2) is soaked 150s in solution A, and taking-up drains.
(4) be immersed in B solution: be dissolved in octane by 2.0g pyromellitic trimethylsilyl chloride, stirring and dissolving obtains B solution.The alloy ultrafiltration membrane having soaked solution A in step (3) is placed in B solution and carries out interfacial reaction, reaction time 100s, preserve in deionized water after taking out the residual cyclohexane of air-dry face.
Embodiment 5
(1) prepared polymer solution: 20g polyethylene glycol and 20g m-phenylene diamine (MPD) are scattered in 780g methyl-sulfoxide, 30min is stirred at 1600 rpm with mechanical agitator, thereafter 120g polysulfones and 60g sulfonated polyether sulfone are dispensed into wherein, and intensification is 30 DEG C, stirring and dissolving under 1400rpm rotating speed, dissolution time 24h, deaeration vacuum-80KPa.Thing to be polymerized dissolves completely, gained solution is placed in vacuum drying oven standing and defoaming, inclined heated plate 48h.
(2) to be separated removal solvent with non-solvent induction: by the alloy ultrafiltration supporting layer of preparation in step (1), with deaeration, solution scraper even application is on non-woven fabrics base material completely, and the deionized water being placed in 50 DEG C is carried out process and obtained alloy ultrafiltration membrane; Gained alloy ultrafiltration membrane deionized water continues rinsing to remove residual solvent, and preserves in deionized water.
(3) be immersed in solution A: 45g piperazine and 2g NaOH are dissolved in 953g deionized water, stirring and dissolving obtains solution A completely.The alloy ultrafiltration membrane of preparation in step (2) is soaked 300s in solution A, and taking-up drains.
(4) be immersed in B solution: be dissolved in heptane by 2.0g pyromellitic trimethylsilyl chloride, stirring and dissolving obtains B solution.The alloy ultrafiltration membrane having soaked solution A in step (3) is placed in B solution and carries out interfacial reaction, reaction time 100s, preserve in deionized water after taking out the residual cyclohexane of air-dry face.
Get comparative film and the embodiment of the present invention 1 ~ 5 gained complex reverse osmosis membrane, film its separating property is tested, the operating condition of employing is: feed liquor is the sodium-chloride water solution of 4000mg/l, and operating pressure is 225psi, operating temperature is 20 DEG C, and solution ph is 6.8; And obtain salt rejection rate (R) and water flux (F) by the computing formula of salt rejection rate and water flux.Getting supporting layer is polysulfone porous membrane, and desalination layer is Wholly aromatic polyamide (m-phenylene diamine (MPD) and pyromellitic trimethylsilyl chloride), thickness be 0.18 RO film be comparative example, obtain its salt rejection rate (R) and water flux (F).Salt rejection rate and water flux are two important parameters evaluating reverse osmosis membrane, and the salt rejection rate of reverse osmosis membrane and the size of water permeation flux directly decide the efficiency of reverse osmosis process.Salt rejection rate (R) refers under certain operating conditions, feeding liquid salinity (Cf) and the difference of salinity (Cp) and the ratio of feeding liquid salinity (Cf) in penetrating fluid, and its computing formula is:
water flux (F) is under certain operating conditions, and through the volume (V) of the water of per membrane area (A) in the unit interval (t), its unit is GFD, and its computing formula is:
result is shown in table 1.
The ultrafiltration layer that in the present invention, comparative film and embodiment 1 ~ 5 are addressed and the peel strength of nonwoven layer adopt tensilon to test.
Comparative film (common alloy ultrafiltration membrane) is prepared by following method:
(1) 20g glycol monoethyl ether and 20g m-phenylene diamine (MPD) are scattered in 780g DMA, stir 30min at 1600 rpm with mechanical agitator, thereafter 180g polysulfones is dispensed into wherein, and heat up, stirring and dissolving under 80 degree and 1400rpm rotating speed, dissolution time 12h.Thing to be polymerized dissolves completely, gained solution is placed in vacuum drying oven standing and defoaming, inclined heated plate 10h.Then, by deaeration completely solution scraper even application on non-woven fabrics base material, obtain alloy ultrafiltration membrane with carrying out process in the deionized water being placed on 20 degree.Gained alloy ultrafiltration membrane deionized water continues rinsing to remove residual solvent, and preserves in deionized water.
(2) 45g m-phenylene diamine (MPD) and 2g NaOH are dissolved in 953g deionized water, stirring and dissolving obtains solution A completely.
(3) be dissolved in cyclohexane by 2.0g pyromellitic trimethylsilyl chloride, stirring and dissolving obtains B solution;
(4) alloy ultrafiltration membrane of preparation in (1) is soaked 30s in solution A, taking-up drains;
(5) alloy ultrafiltration membrane having soaked solution A in (4) is placed in B solution and carries out interfacial reaction, reaction time 20s, preserve in deionized water after taking out the residual cyclohexane of air-dry face.
Alloy ultrafiltration performance index in table 1 diffusion barrier
As shown in Table 1, the composite separating film with alloy ultrafiltration layer of embodiments of the invention 1 ~ 5 gained no matter in non-woven fabrics extent of exfoliation, or in salt rejection rate, is all obviously better than comparative film, i.e. common alloy ultrafiltration membrane at ultrafiltration layer.
Get comparative film and the embodiment of the present invention 1,2 gained complex reverse osmosis membrane, carry out the test of face anti-scuffing function: adopt 5 × 5cm
2sheet rubber, under 0.5MPa pressure, scraping face, scraping number of times 5 times; To dye scraping the face rhodamine after wiping 20s, after fully cleaning face by deionized water, judge anti-scuffing function according to dye level, colourless or slight dyeing shows that resistance to marring is strong.As shown in Figure 1, Figure 2, Figure 3 shows, Fig. 1 is the resistance to marring result of the test of embodiment 1, Fig. 2 is the resistance to marring result of the test of embodiment 2, Fig. 3 is the resistance to marring result of the test of comparative film, contrasted from Fig. 1,2,3, the composite separating film resistance to marring of embodiment of the present invention gained is outstanding, and the resistance to marring of comparative film is obviously be not as good as composite separating film of the present invention.
Claims (5)
1. there is a preparation method for the composite separating film of alloy ultrafiltration supporting layer, it is characterized in that: mainly comprise the following steps:
(1) prepared polymer solution: pore former and reactive monomer are placed in solvent in proportion, stir, then two kinds and above polymer raw material are placed in solvent in proportion, it is 30 ~ 90 DEG C that rapid stirring also heats up, dissolve 1 ~ 24h, gained solution left standstill vacuum defoamation 4 ~ 48h, deaeration vacuum-80KPa, obtains polymer solution; In solution, the total content of polymer is 5 ~ 30wt%, and reactive monomer content is 0.1 ~ 20wt%, and porogen content is 0.5 ~ 20wt%;
(2) induce with non-solvent the removal solvent that is separated: be coated on non-woven fabrics by resulting polymers dissolution homogeneity in step (1), be placed in non-solvent, temperature is 10 ~ 50 DEG C, and induction forms alloy ultrafiltration supporting layer after being separated and removing solvent;
(3) be immersed in solution A: alloy ultrafiltration supporting layer described in step (2) is soaked in 1 ~ 300s in solution A, take out after leaving standstill certain hour, drain surface water drops, wherein solution A is mixed with by the m-phenylene diamine (MPD) of 0.1 ~ 5wt% and/or piperazine monomer and water;
(4) be immersed in B solution: the alloy ultrafiltration membrane that will process through step (3) contacts 1 ~ 100s with B solution, form aramid layer, after air-dry surface solvent, obtain composite separating film; Wherein, B solution be by the pyromellitic trimethylsilyl chloride monomer of 0.01 ~ 5wt% and solvent formulated, solvent for use is any one or several in cyclohexane, heptane, octane, ISOPAR-E, ISOPAR-G and ISOPAR-L;
In described step (1) in polymer raw material, wherein one is polysulfones, also comprises any one or several in polyether sulfone, PPSU, sulfonated polyether sulfone, polyvinyl chloride, polyimides, Triafol T, cellulose diacetate and Kynoar in addition;
When polymer raw material is made up of polysulfones and polyether sulfone, wherein the weight ratio of polyether sulfone in alloy-layer is 0.1 ~ 20wt%;
When polymer raw material is made up of polysulfones and PPSU, wherein the weight ratio of PPSU in alloy-layer is 0.01 ~ 10wt%;
When polymer raw material is made up of polysulfones and sulfonated polyether sulfone, wherein the weight ratio of sulfonated polyether sulfone in alloy-layer is 0.1 ~ 10wt%;
When polymer raw material is made up of polysulfones, polyether sulfone and sulfonated polyether sulfone, wherein the weight ratio of polyether sulfone in alloy-layer is 0.1 ~ 15wt%, and the weight ratio of sulfonated polyether sulfone in alloy-layer is 0.1 ~ 5wt%;
When polymer raw material is made up of polysulfones and Triafol T, wherein the weight ratio of triacetate fiber in alloy-layer is 0.1 ~ 15wt%;
When polymer raw material is made up of polysulfones and cellulose diacetate, wherein the weight ratio of cellulose diacetate in alloy-layer is 0.1 ~ 20wt%;
When polymer raw material is made up of polysulfones, Triafol T and cellulose diacetate, wherein the weight ratio of Triafol T in alloy-layer is 0.1 ~ 10wt%; The weight ratio of diacetate fiber in alloy-layer is 0.1 ~ 20wt%;
Reactive monomer in described step (1) is amine monomers, acyl chloride monomer and containing any one or several in-NCO monomer;
Solvent in described step (1) refers to any one or several in DMF, DMA, N, N-dimethyl pyrrolidone, acetone and methyl-sulfoxide;
Pore former in described step (1) refers to any one or several in sodium chloride, lithium chloride, PVP, polyethylene glycol and glycol monoethyl ether;
In described step (2) for inducing the non-solvent be separated to be any one or several in water, ethanol, isopropyl alcohol, the tert-butyl alcohol and glycerine.
2. a kind of preparation method with the composite separating film of alloy ultrafiltration layer according to claim 1, it is characterized in that: the concentration of described amine monomers is 0.1 ~ 10wt%, concrete amine monomers refers to ethylenediamine, triethylamine, hexamethylene diamine, p-phenylenediamine (PPD), o-phenylenediamine, m-phenylene diamine (MPD), piperazine, O-phthalic amine, p dimethylamine, m-xylene diamine, 2, any one or several in 2 '-benzidine sulfonic acid.
3. a kind of preparation method with the composite separating film of alloy ultrafiltration layer according to claim 1, it is characterized in that: the concentration of described acyl chloride monomer is 0.1 ~ 10wt%, concrete acyl chlorides monomer refers to any one or several in acyl chlorides of pyromellitic trimethylsilyl chloride, paraphthaloyl chloride, m-phthaloyl chloride, o-phthaloyl chloride and biphenyl four.
4. a kind of preparation method with the composite separating film of alloy ultrafiltration layer according to claim 1, is characterized in that: the molecular configuration of the described monomer containing-NCO functional group is characterized as NCO-R-NCO, and wherein R is organic group, and carbon containing number is 2 ~ 18; Its concentration in alloy ultrafiltration supporting layer is 0.01 ~ 10wt%.
5. a kind of preparation method with the composite separating film of alloy ultrafiltration layer according to any one of claim 1-4 prepares the composite separating film with alloy ultrafiltration layer, it is characterized in that: comprise nonwoven layer, ultrafiltration supporting layer and aramid layer; Described ultrafiltration supporting layer is alloy ultrafiltration supporting layer, and containing two kinds and above polymer and reactive monomer, and reactive monomer is identical with any one or several in synthesizing polyamides layer monomer used; Alloy ultrafiltration supporting layer is induced to be separated by the solution coating carried out in nonwoven surface and the non-solvent carried out in non-solvent and is prepared from; Described aramid layer to be contacted with the solution containing acyl chlorides monomer by the solution containing amine monomers and is formed on alloy ultrafiltration supporting layer.
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| CN104117288B (en) * | 2013-04-25 | 2017-07-18 | 财团法人工业技术研究院 | Filter material and method for producing same |
| CN105080352B (en) * | 2014-04-24 | 2017-09-26 | 中国石油化工股份有限公司 | A kind of complex reverse osmosis membrane and preparation method |
| CN103962018A (en) * | 2014-05-07 | 2014-08-06 | 云南云天化股份有限公司 | Polyvinylidene fluoride reinforced microporous membrane and preparation method thereof |
| CN104043341A (en) * | 2014-06-23 | 2014-09-17 | 南通惠然生物科技有限公司 | High-flux antioxidant filter membrane |
| CN105576176B (en) * | 2016-01-29 | 2018-01-30 | 中南大学 | A kind of preparation method of high security lithium ion battery diaphragm |
| CN105727763B (en) * | 2016-03-07 | 2018-05-22 | 天津大学 | A kind of preparation method of fluorine-containing polyamide composite nanofiltration membrane |
| CN108489895A (en) * | 2018-03-20 | 2018-09-04 | 时代沃顿科技有限公司 | A kind of detection method and detecting instrument for the anti-wiping property value of reverse osmosis membrane |
| CN110201562A (en) * | 2019-05-27 | 2019-09-06 | 武汉纳霏膜科技有限公司 | A kind of preparation method of chlorine-resistant anti-pollution reverse osmosis membrane |
| CN111632502A (en) * | 2020-06-05 | 2020-09-08 | 上海恩捷新材料科技有限公司 | Non-woven fabric substrate supported polyethylene nanofiltration membrane |
| WO2022183751A1 (en) * | 2021-03-05 | 2022-09-09 | 中国石油化工股份有限公司 | Double-continuous high-pass polymer ultrafiltration membrane, preparation method therefor, and application thereof |
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