CN104084057A - Preparation method of diffusion dialysis cation exchange membrane - Google Patents
Preparation method of diffusion dialysis cation exchange membrane Download PDFInfo
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- CN104084057A CN104084057A CN201410364509.4A CN201410364509A CN104084057A CN 104084057 A CN104084057 A CN 104084057A CN 201410364509 A CN201410364509 A CN 201410364509A CN 104084057 A CN104084057 A CN 104084057A
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- 239000012528 membrane Substances 0.000 title claims abstract description 64
- 238000005341 cation exchange Methods 0.000 title claims abstract description 49
- 238000000502 dialysis Methods 0.000 title claims abstract description 28
- 238000009792 diffusion process Methods 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 19
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 57
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 57
- 239000007788 liquid Substances 0.000 claims abstract description 30
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 25
- 229910000077 silane Inorganic materials 0.000 claims abstract description 17
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 238000000576 coating method Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 19
- 239000000376 reactant Substances 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 229960005070 ascorbic acid Drugs 0.000 claims description 6
- 235000010323 ascorbic acid Nutrition 0.000 claims description 6
- 239000011668 ascorbic acid Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010526 radical polymerization reaction Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 230000001172 regenerating effect Effects 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Substances 0.000 claims description 3
- 230000005587 bubbling Effects 0.000 claims description 3
- QATBRNFTOCXULG-UHFFFAOYSA-N n'-[2-(methylamino)ethyl]ethane-1,2-diamine Chemical compound CNCCNCCN QATBRNFTOCXULG-UHFFFAOYSA-N 0.000 claims description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- RGHQKFQZGLKBCF-UHFFFAOYSA-N 2-bromoethyl acetate Chemical group CC(=O)OCCBr RGHQKFQZGLKBCF-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- -1 by initator Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N ethyl butyrate Chemical class CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229940042795 hydrazides for tuberculosis treatment Drugs 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010257 thawing Methods 0.000 claims description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 2
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical group Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 150000007984 tetrahydrofuranes Chemical group 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 22
- 238000005342 ion exchange Methods 0.000 abstract description 16
- 238000000926 separation method Methods 0.000 abstract description 14
- 238000004132 cross linking Methods 0.000 abstract description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000008961 swelling Effects 0.000 abstract description 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 230000004913 activation Effects 0.000 abstract 1
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- 230000008929 regeneration Effects 0.000 abstract 1
- 238000011069 regeneration method Methods 0.000 abstract 1
- 230000027756 respiratory electron transport chain Effects 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- 239000002253 acid Substances 0.000 description 9
- 239000003513 alkali Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004721 Polyphenylene oxide Substances 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 7
- 229920001577 copolymer Polymers 0.000 description 7
- 229920006380 polyphenylene oxide Polymers 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001299 aldehydes Chemical group 0.000 description 6
- 239000002699 waste material Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 230000010148 water-pollination Effects 0.000 description 5
- 229910008051 Si-OH Inorganic materials 0.000 description 4
- 229910006358 Si—OH Inorganic materials 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000003011 anion exchange membrane Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical group [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- WDAXFOBOLVPGLV-UHFFFAOYSA-N ethyl isobutyrate Chemical class CCOC(=O)C(C)C WDAXFOBOLVPGLV-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229940059939 kayexalate Drugs 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
本发明公开了一种扩散渗析阳离子交换膜的制备方法，其特征在于：将含有双键和-SO3Na基团的单体通过电子转移活化再生催化剂原子转移自由基聚合(ARGET-ATRP)得到聚电解质，将该聚电解质与膜基体聚乙烯醇共混，并用硅烷偶联剂交联得到涂膜液，涂膜后干燥、热处理得到阳离子交换膜。本发明的方法利用聚乙烯醇的韧性和强度赋予涂膜液成膜性好、膜柔韧性佳、抗撕裂等性能；利用PVA含有的大量羟基(-OH)和高亲水性赋予膜对水合离子如OH-的高渗析通量；通过聚电解质的加入将离子交换基团引入膜中，赋予膜高渗透量、离子选择分离特性；再用硅烷进行交联，可以克服膜溶胀度高的缺点。
The invention discloses a method for preparing a diffusion dialysis cation exchange membrane, which is characterized in that: monomers containing double bonds and -SO 3 Na groups are obtained through electron transfer activation regeneration catalyst atom transfer radical polymerization (ARGET-ATRP) Polyelectrolyte, the polyelectrolyte is blended with polyvinyl alcohol as a membrane matrix, and cross-linked with a silane coupling agent to obtain a coating solution, which is then dried and heat-treated to obtain a cation exchange membrane. The method of the present invention utilizes the toughness and strength of polyvinyl alcohol to impart properties such as good film-forming properties, good film flexibility, and tear resistance to the coating liquid; utilizes a large amount of hydroxyl (-OH) contained in PVA and high hydrophilicity to impart to the film High dialysis flux of hydrated ions such as OH- ; ion exchange groups are introduced into the membrane by adding polyelectrolyte, endowing the membrane with high permeability and ion-selective separation characteristics; cross-linking with silane can overcome the high degree of membrane swelling shortcoming.
Description
Technical field
The invention belongs to amberplex preparing technical field, particularly polyelectrolyte preparation, blend, crosslinked with silicane are prepared the method for diffusion dialysis cation-exchange membrane.
Background technology
In modern industry production process, can produce a large amount of spent acid salkali waste, if without suitably processing directly discharge, not only cannot effectively utilize the useful resources in waste liquid, also can cause serious infringement to environment and water source, biology.Ionic membrane is applied to diffusion dialysis (DD), can effectively separates and waste acid recovery salkali waste.DD process only, using film both sides feed liquid concentration difference as driving force, has the features such as continuous, simple, efficient and economic environmental protection.DD processes spent acid, needs anion-exchange membrane; Process salkali waste, need cation-exchange membrane.These two kinds of ionic membranes are all generally as parent, because of comparatively hydrophobic of its main body, so very little to the dialysis flux of acid or alkali taking polyphenylene oxide, polystyrene, polysulfones, polyether sulfone etc.Aspect acid recovery, periodical " Journal of Membrane Science " 347 volume 240-249 pages in 2010 have reported that business anion-exchange membrane (DF-120) is in static DD process, to the dialysis flux of HCl in 0.002-0.009m/h scope; Periodical " China YouSe Acta Metallurgica Sinica " 18 volume 88-91 pages in 2008 are reported in dynamic DD process, 500m
2only 6 tons of left and right of polyphenylene oxide (PPO) the anion-exchange membrane acid solution treating capacity of a day.Aspect alkali recovery, due to OH
-migratory activity is significantly lower than H
+, the migration velocity in film is slower, so dialysis flux is lower.The industrialization that DD reclaims for alkali at present and research report are wanted much less compared with acid recovery, wherein periodical " Journal of Membrane Science " the 347th volume 240-249 page in 2010 has reported that PPO business cation-exchange membrane is in static DD process, is only 0.0014m/h left and right to the dialysis flux of NaOH.Periodical " membrane science and technology " calendar year 2001s 21, volume 37-43 page reported that such film is for dynamic DD process, and the treating capacity of a day is estimated 1 ton of less than, can not be applied to actual separation occasion.Integrate and see, existing amberplex, particularly cation-exchange membrane are existing obvious defect and deficiency aspect DD processing salkali waste.For this reason, need to prepare the cation-exchange membrane of high dialysis flux.In addition, the long-term operation of DD also needs film to have higher stability.
Polyvinyl alcohol (PVA) is a kind of macromolecular material with good hydrophily, stain resistance and filming performance, and the higher and environmental friendliness of its mechanical performance, heat endurance and chemical stability, is commonly used to the active cortex as composite membrane at present.In PVA, contain a large amount of hydroxyl (OH), hydrophily is high, little to the osmotic resistance of hydrated ion, and can promote H by hydrogen bond action
+and OH
-the transmission of ion, institute is for having good dialysis flux in DD process.But the hydrophily of PVA and a large amount of-OH group also make its water-soluble rising property strengthen simultaneously, cause the stability of film, selectively decline, in actual applications cannot stable for extended periods of time.On the other hand owing to not containing ion-exchange group in PVA, so cannot directly be used for DD field as ionic membrane.
In order to improve the stability of PVA, existing researcher carries out cross-linking modified with aldehyde to PVA.Periodical " membrane science and technology " 20 volume 23-25 page reports in 2000 are cross-linked PVA and polyacrylonitrile compound film with glyoxal, glutaraldehyde, terephthalaldehyde, separate alcohol/water for infiltration evaporation.The toxicity of aldehyde is larger, and in the time that crosslinking degree increases, the flux of film declines, this is to be the hydroxyl generation aldolisation in aldehyde and PVA because aldehyde is cross-linked, so can significantly consume the hydroxyl in PVA, make to rely on hydrogen bond between macromolecular chain and the interaction that occurs weakens.
On the other hand, in order to introduce ion-exchange group in PVA film, there is researcher by PVA and polystyrolsulfon acid (PSS) or kayexalate (PSSNa) blend.Periodical " Journal of Applied Polymer Science " 88 volume 79-87 pages in 2003 utilize PVA and PSSNa blend to make evenly pliable and tough film, and this film has good electric conductivity and mechanical performance.But because film is cross-linked, so the swellability of film does not effectively overcome, cannot be used for water treatment field.Periodical " Journal of Membrane Science " 463 volume 173-182 pages in 2014 have been reported by PVA and PSSNa blend and with glutaraldehyde and have been cross-linked, have been coated in porous polysulfones (PSf) membrane surface and obtain composite membrane.In this composite membrane, PVA-PSSNa is only as surperficial cortex, and film main body is still hydrophobicity film, and the effect of improvement is limited.In addition, aldehyde crosslinking method can consume the hydroxyl in PVA equally.So film mainly, as nanofiltration, is not suitable for DD field.Periodical " Solid State Ionics " 253 volume 189-194 pages in 2013 are by PVA and polystyrolsulfon acid (PSS) blend, and use succinic acid (SA) is crosslinked at 180-200 DEG C.Under sour catalysis, PVA carries out dehydration condensation and generates two keys and ehter bond, reaches cross-linking effect.But crosslinked caudacoria becomes fine and close, and PVA chain pliability reduces, and hydroxyl loss is more.This kind of film is used for fuel cell mainly as proton conductive membrane, is not suitable for DD field.
In order to make PVA successfully for DD field, periodical " Desalination " 304 volume 25-32 pages in 2012 have been introduced SSNa and γ-methacryloxypropyl trimethoxy silane (KH570) have been made to many siliceous copolymers by free-radical polymerized, then by PVA and many siliceous copolymers blend masking.This film can be processed NaOH/Na for DD
2wO
4mixed liquor, reaches higher alkali dialysis flux (0.0102-0.0111m/h) and separation factor (16.9-18.5).Due to contain-SO of SSNa
3na group, is ionic comonomer, so larger with the difficulty of KH570 copolymerization, product structure and molecular weight cannot accurately be controlled, and molecular weight is lower.In addition, in many siliceous copolymers, also contain the KH570 composition of nonionic, so compared with PSSNa, ion exchange capacity is lower.More crucial, in many siliceous copolymers, hold concurrently containing a large amount of-SO
3na and-Si (OR)
3group, in polymerization and preservation process-SO
3na can catalysis-Si (OR)
3hydrolysis, condensation, so easily self intersection connection forms gel, preparation and store difficulty, is unfavorable for amplifying and produces.
Summary of the invention
The present invention is intended to make up above-mentioned deficiency, and a kind of preparation method of cation-exchange membrane is provided, and technical problem to be solved is how to prepare that dialysis flux is high, selectively good and good stability, diffusion dialysis cation-exchange membrane that swellability is low.
Technical solution problem of the present invention, adopts following technical scheme:
The preparation method of diffusion dialysis cation-exchange membrane of the present invention, its feature is: will contain two keys and-SO
3the monomer of Na group carries out electronics and shifts activating and regenerating catalyst atoms transferring free-radical polymerization (ARGET-ATRP), obtains polyelectrolyte; By even the aqueous solution blend of described polyelectrolyte and film matrix polyvinyl alcohol (PVA), then add silane coupler crosslinked, obtain coating liquid; By described coating liquid film, be then dried, heat treatment, obtain cation-exchange membrane.
Preparation method of the present invention, its feature is also:
To contain two keys and-SO
3the monomer of Na group carries out electronics to be shifted activating and regenerating catalyst atoms transferring free-radical polymerization to obtain polyelectrolyte is to carry out as follows:
Step 1: in polymerization pipe, add solvent, by initator, catalyst, part and contain two keys and-SO
3the monomer of Na group is dissolved in described solvent, then in described polymerization pipe, passes into inert gas, bubbling 1-2h;
Step 2: reactant in polymerization pipe is refrigerated to solid-state, being then evacuated to vacuum in polymerization pipe is 0.05-100Pa, and keeps 2-5min, then pass into inert gas and return to normal pressure and keep 3min, finally reactant in polymerization pipe is thawed to liquid state;
Step 3: repeating step 2 twice again;
Step 4: add again reducing agent in polymerization pipe; and at polymerization pipe described in inert gas shielding lower seal, at 60-120 DEG C, stir polymerization 12-48h, stop polymerization; by product in polymerization pipe successively through precipitation, centrifugal, 60 DEG C be dried to constant weight, obtain polyelectrolyte.
Described in step 1, solvent is the mixed solvent of dimethyl sulfoxide (DMSO) or the first alcohol and water formation that 1:1 mixes by volume; Described initator is selected from bromoethyl acetate (EBrA), alpha-brominated ethyl butyrate (EBrB) or alpha-brominated different acetoacetic ester (EBiB); Described catalyst is selected from copper bromide (CuBr
2), copper chloride (CuCl
2) or iron chloride (FeCl
3); Described part is selected from bipyridine (bpy), N, N, N', N', N " five methyl diethylentriamine (PMEDTA) or three-(N, N-dimethylaminoethyl) amine (Me
6tREN); Described contain two keys and-SO
3the monomer of Na group is SSS (SSNa);
Described in step 4, reducing agent is selected from ascorbic acid (AsAc), hydrazides or stannous octoate;
The mol ratio of described initator, catalyst, part and monomer is 20-50:1:50:200-800; The quality of described monomer and the volume ratio of described solvent are 1g:10-40ml; The mol ratio of described catalyst and described reducing agent is 1:5-10.
Described inert gas is selected from argon gas, nitrogen or helium;
In step 2, reactant in polymerization pipe being refrigerated to solid-state is that reactant in polymerization pipe is cooled to below by liquid and is transformed into solid completely at-100 DEG C;
In step 2, reactant in polymerization pipe being thawed to liquid state is that polymerization pipe is placed at 10-40 DEG C, until reactant is liquid by solid-state thawing completely in polymerization pipe;
Described in step 4, stopping polymerization is that the polymerization pipe having sealed is broken, and reactant in polymerization pipe is exposed in air, and polymerization is stopped.
Described in step 4, precipitation is that the product in polymerization pipe is added drop-wise in precipitating reagent and forms and precipitate; Described precipitating reagent is selected from oxolane (THF) or absolute ether.
The mass ratio of described polyelectrolyte and described film matrix polyvinyl alcohol is 0.5-1.5:1; By the uniform step of aqueous solution blend of described polyelectrolyte and film matrix polyvinyl alcohol be: first prepare mass concentration and be the aqueous solution of 5% film matrix polyvinyl alcohol, then described polyelectrolyte at room temperature joined in the aqueous solution of described film matrix polyvinyl alcohol and stir 15-30min.
The mass ratio of described polyelectrolyte and described silane coupler is 1:1-2.5; Described silane coupler is selected from γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560), tetraethoxysilane (TEOS), (3-aminopropyl) triethoxysilane (A-1100) or γ-methacryloxypropyl trimethoxy silane (KH570); Described being cross-linked is at 25-60 DEG C of stirring reaction 20min-6h.
Described film is that described coating liquid is coated on polyfluortetraethylene plate;
Described dry be by the polyfluortetraethylene plate that is coated with coating liquid be placed in circulation of air place until coating liquid exsiccation film forming film is taken off from tetrafluoroethene plate;
Described heat treatment is that the film of taking off from polyfluortetraethylene plate is first heated to 0.5-2h at 30-60 DEG C, then is warming up to 120-140 DEG C with the speed of 5-20 DEG C/h, and is incubated 2-5h.
Compared with the prior art, beneficial effect of the present invention is embodied in:
The present invention is by PVA and polyelectrolyte PSSNa blend, PVA has that hydrophily is high, stain resistance is high, filming performance is good, mechanical performance, heat endurance and chemical stability advantages of higher, in PVA, contain in addition a large amount of-OH group, this group belongs to high-hydrophilic group, and-can form hydrogen bond between OH group, can promote OH in DD process
-transport, cause it in DD process, to have good dialysis flux, this has just met DD and has reclaimed the requirement of alkali lye to dialysis flux; Because PSSNa contains ion-exchange group-SO
3na, introduce PSSNa in PVA film, just given film high selective;
The present invention adopts the crosslinked PVA of silane coupler and PSSNa blend film first, and the crosslinked toxicity of conventional aldehyde is large, and significantly consume in PVA-OH base; Silane coupler can be hydrolyzed, condensation, self forms Si-O-Si inorganic network, can also be crosslinked by Si-O-C key and PVA forming section, thereby erect " molecular bridge " between inorganic substances and the interface of organic substance, improve stability, the solvent resistance of film, overcome the high shortcoming of PVA film swellability; The part consumption of can make up in PVA-OH group of the Si-OH that silane hydrolyzate generates, has also promoted hydration OH in DD process
-the transmission of ion, thus keep the permeation flux of film to alkali;
The present invention adopts ARGET-ATRP to prepare PSSNa, compared with radical polymerization, can obtain more regular product structure and the molecular weight of Geng Gao, in addition, does not contain-Si (OR) in PSSNa
3group, forms gel so be difficult for self intersection connection, can preserve for a long time, and this point is significant to amplifying production.
Brief description of the drawings
Fig. 1 is the infrared spectrogram of the cation-exchange membrane for preparing of the embodiment of the present invention 1;
Fig. 2 is the Thermal Chart of the cation-exchange membrane for preparing of the embodiment of the present invention 1;
Fig. 3 is the Thermal Chart of reference film 2 in the embodiment of the present invention 2;
Fig. 4 is the infrared spectrogram of the cation-exchange membrane for preparing of the embodiment of the present invention 3;
Fig. 5 is the Thermal Chart of the cation-exchange membrane for preparing of the embodiment of the present invention 3;
Fig. 6 is the infrared spectrogram of the cation-exchange membrane for preparing of the embodiment of the present invention 4;
Fig. 7 is the Thermal Chart of the cation-exchange membrane for preparing of the embodiment of the present invention 4.
Detailed description of the invention
Further describe by the following examples the preparation method of cation-exchange membrane of the present invention.
Embodiment 1:
The present embodiment is prepared diffusion dialysis cation-exchange membrane through following steps:
1, the SSS of purchasing (SSNa) is purified taking ethanol/water (volume ratio of ethanol and water is as 9:1) as solvent recrystallization.In polymerization pipe, add 30ml methanol-water solution (volume ratio 1:1).Continue to add the alpha-brominated ethyl isobutyrate of 0.430ml (EBiB), 0.0034g copper bromide (CuBr
2), " above four kinds of material mol ratios are 20:1:50:700 for five methyl diethylentriamine (PMDETA), 2gSSNa, are mixed to solid and dissolve completely, after liquid clarification homogeneous, pass into 1h nitrogen, bubbling deoxygenation for 0.156mlN, N, N', N', N.
By polymerization pipe with-198 DEG C of liquid nitrogen frozens until in pipe reactant be all transformed into solid by liquid, then vacuumize with vavuum pump, until vacuum is 0.06Pa, keep 3min.Pass into again nitrogen to recovering normal pressure, keep 3min, finally thaw at 25 DEG C again, until solid is melted into liquid completely.Continuation liquid nitrogen frozen, so, after three " freezing-to vacuumize-Tong nitrogen-thaw " cyclic processes, can remove the oxygen in reactant.
In polymerization pipe, add the ascorbic acid (AsAc) of 0.013g, CuBr
2and the molar ratio between AsAc is 1:5.At nitrogen protection lower seal polymerization pipe, be placed in 80 DEG C of oil bath pan stirring reactions, after 24h, break polymerization pipe, reactant in polymerization pipe is exposed in air, reaction stops.Product in tube sealing is added drop-wise to precipitation in oxolane (THF), by centrifuge centrifugal go out product be placed in 60 DEG C of baking ovens and be dried to constant weight, obtain polyelectrolyte PSSNa.
2, PVA is mixed with to the homogeneous aqueous solution of 5% (mass concentration), gets 0.5gPSSNa and at room temperature join in 20mlPVA solution, after stirring 20min, obtain the solution of homogeneous clarification.
3,1g tetraethoxysilane (TEOS) is joined in the uniform solution of above polyelectrolyte and PVA, be placed in 60 DEG C of oil bath pan magnetic agitation 6h, obtain the coating liquid of homogeneous.Coating liquid is coated on polyfluortetraethylene plate, is placed in fume hood inner drying film forming, intactly film is taken off.Film is first heated to 1h at 60 DEG C, then be warming up to 130 DEG C with the speed of 10 DEG C/h, keep 4h, obtain cation-exchange membrane.
In addition, get the PVA aqueous solution of 20ml 5% as coating liquid, process and above similarly film, dry run, obtain PVA blank film.This blank film is through formaldehyde crosslinking, and the film obtaining is as reference film 1.Wherein formaldehyde crosslinking is that film is immersed in to the formaldehyde containing 5.41g, in the mixed solution of 12.5g sulfuric acid and 47g water, in 60 DEG C of reaction 2h.
The mean molecule quantity of testing polyelectrolyte PSSNa by GPC is 5310, and polydispersity index PDI value is 1.55.Periodical " Desalination " 304 volume 25-32 pages in 2012 carry out free-radical polymerized to SSNa and KH570, DD film is prepared in the many siliceous copolymers and the PVA blend that obtain, but does not report the molecular weight of many siliceous copolymers.As a comparison, periodical " Journal of Membrane Science " 399-400 phase 16-27 page in 2012 reports that p-chloromethyl styrene (VBC) and KH570 carry out free-radical polymerized, wherein VBC is not containing ion-exchange group, so copolymerization difficulty should be low compared with SSNa, but copolymerization product is just obviously divided into solid and liquid two-phase in precipitation, purification process, there were significant differences for two-phase molecular weight, is respectively 3565 and 733.By contrast, illustrate that PSSNa prepared by the present embodiment has higher molecular weight, molecular weight distribution is also more regular.
Cation-exchange membrane and reference film 1 are carried out to diffusion dialysis (DD) test process of alkali: film is immersed in to 1.0mol/LNaOH and 0.1 mol/LNa
2wO
42h in mixed solution, then, with deionized water washing, packs in static diffusion dialysis (DD) device.Film one side is 100mlNaOH (1.0mol/L) and Na
2wO
4(0.1 mol/L) mixed solution, opposite side is 100ml deionized water.In order to reduce the impact of concentration polarization, it is identical that the speed that stir two Room keeps, sampling and testing after 1h.OH in solution
-ion concentration is measured with HCl titration method, WO
4 2-ion concentration rhodanate metric measurement.In above process, DD device and method of testing are with reference to periodical literature " Separation and Purification Technology " 115 volume 216-223 page reports in 2013.
In addition, cation-exchange membrane is carried out to infrared, hot analytical test, and carry out water content, ion exchange capacity test, result is as follows.
Fig. 1 is the infrared spectrum of the prepared cation-exchange membrane of the present embodiment, in figure, and～3450cm
-1for PVA or-Si-OH is upper-the vibration performance peak of OH ,～2940cm
-1for-CH
2absworption peak ,～1648cm
-1be-CH
3,-CH
2-, the stretching vibration peak of=CH-group ,～1120cm
-1be-stretching vibration peak of Si-O-Si-.～1040cm
-1with～1200cm
-1be-SO
3the stretching vibration peak of Na.This shows PVA and PSSNa success blend, and silane TEOS has also played effective crosslinked action.
Fig. 2 is the Thermal Chart of the prepared cation-exchange membrane of the present embodiment, and result shows under air atmosphere, and cation-exchange membrane heat decomposition temperature (Td, temperature weightless 5% time) is 118.6 DEG C.
Water content test shows that cation-exchange membrane water content is 120.7%.
Ion exchange capacity measurement result: cation exchange capacity is 1.24mmol/g.As a comparison, periodical " Desalination " 304 volume 25-32 pages in 2012 are reported the film that PVA and the blend of many siliceous copolymers obtain, and its cation exchange capacity is 0.72-1.05mmol/g.
DD result shows: cation-exchange membrane is to OH
-ionodialysis flux is 0.0208m/h, and separation factor is 18.41.Reference film 1 is to OH
-ionodialysis flux is 0.0080m/h, and separation factor is 9.25.
The above analysis result, the cation-exchange membrane that known the present embodiment obtains, has higher ion exchange capacity, hydrophily and heat endurance.Than reference film 1, this film is for DD NaOH separating/Na
2wO
4time, dialysis flux and separation selectivity obviously improve, and dialysis flux and the separation selectivity that can significantly improve film of adding of the PSSNa that contains ion-exchange group is described.
Embodiment 2
The preparation method of the present embodiment cation-exchange membrane is with embodiment 1, and different is the PVA aqueous solution blend of getting 1gPSSNa and 20ml 5%, and the mass ratio of PSSNa and PVA is 1:1; Get 1.0608g (3-aminopropyl) triethoxysilane (A-1100) as silane coupler, replace 1.0g TEOS, be cross-linked with the uniform solution of polyelectrolyte, PVA; Cross-linking reaction time shortens to 2h, obtains cation-exchange membrane.
For ease of contrast, take and upper similar process, but crosslinked with formaldehyde crosslinking replacement silane coupler, obtain reference film 2.Wherein, formaldehyde crosslinking process is similar to the respective process of reference film 1 in embodiment 1.
The cation-exchange membrane that the present embodiment is obtained carries out water content and the test of hot water swelling behavior.Water content test shows: water content is 54.83%.The test of hot water swellability shows: the swellbility of 108h caudacoria is 52.75%.Reference film 2 is carried out to hot analytical test, and Fig. 3 is the Thermal Chart of the present embodiment reference film 2, and result shows under air atmosphere, and the heat decomposition temperature (Td, temperature weightless 5% time) of film is only 35.25 DEG C.
Analyze above-mentioned experimental result, the film that known the present embodiment obtains, water content is suitable, and swellbility is low, and still very low through reference film 2 heat endurances of formaldehyde crosslinking, does not improve.In sum, PSSNa-PVA film after A-1100 is crosslinked, swellbility and stability be improved significantly.
Embodiment 3
The present embodiment preparation method is with embodiment 1, and different is to replace 1g TEOS as silane coupler 1.1345g γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane (KH560); Crosslinking time shortens to 20min, obtains cation-exchange membrane.This film is carried out to infrared, water content, hot analysis, ion exchange capacity and DD test.
Fig. 4 is the infrared spectrum of the prepared cation-exchange membrane of the present embodiment, in figure, and～3450cm
-1for PVA or-Si-OH is upper-the vibration performance peak of OH ,～2940cm
-1for-CH
2absworption peak ,～1650cm
-1be-CH
3,-CH
2-, the stretching vibration peak of=CH-group ,～1120cm
-1be-stretching vibration peak of Si-O-Si-.～1040cm
-1with～1201cm
-1be-SO
3the stretching vibration peak of Na.This shows PVA and PSSNa success blend, and silane KH560 has also played effective crosslinked action.
Fig. 5 is the Thermal Chart of the prepared cation-exchange membrane of the present embodiment, and result shows under air atmosphere, and film heat decomposition temperature Td is 150 DEG C.
Water content test shows: water content is 46.85%.
The cation exchange capacity that ion exchange capacity is measured film is 1.64mmol/g, is significantly higher than the respective value (0.72-1.05mmol/g) of the film of periodical " Desalination " 304 volume 25-32 page reports in 2012.
Diffusion dialysis result shows: film is to OH
-ionodialysis flux is 0.014m/h, and separation factor is 25.72.As a comparison, periodical " Separation and Purification Technology " the 115th volume 216-223 page in 2013 has reported that PPO business cation-exchange membrane is to OH
-ionodialysis flux is 0.007m/h, and separation factor is 11.
The above analysis result, the cation-exchange membrane that known the present embodiment obtains, has higher ion exchange capacity, and the water content of film is suitable.With respect to PPO commercial membranes, this film is for DD NaOH separating/Na
2wO
4can obtain excellent dialysis flux and separation selectivity, illustrate that film can effectively improve its application performance through crosslinked with silicane.
Embodiment 4
The present embodiment preparation method is with embodiment 1, and different is to replace 1g TEOS as silane coupler 1.0608g A-1100; Crosslinking time is 2h.
That the cation-exchange membrane that the present embodiment is obtained carries out is infrared, water content, hot analysis, ion exchange capacity and DD test.
Fig. 6 is the infrared spectrum of the prepared cation-exchange membrane of the present embodiment, in figure, and～3450 cm
-1for PVA or-Si-OH is upper-the vibration performance peak of OH ,～2940cm
-1for-CH
2absworption peak ,～1665cm
-1be-CH
3,-CH
2-, the stretching vibration peak of=CH-group ,～1125cm
-1be-stretching vibration peak of Si-O-Si-.～1040cm
-1with～1198cm
-1be-SO
3the stretching vibration peak of Na.This shows PVA and PSSNa success blend, and silane A-1100 has also played effective crosslinked action.
Fig. 7 is the Thermal Chart of the prepared cation-exchange membrane of the present embodiment, and result shows under air atmosphere, and film heat decomposition temperature (Td, temperature weightless 5% time) is 112 DEG C.
Water content test shows: water content is 55.22%.
The cation exchange capacity that ion exchange capacity is measured film is 1.03mmol/g.
Diffusion dialysis result shows: cation-exchange membrane is to OH
-ionodialysis flux is 0.0072m/h, and separation factor is 16.77.
The above analysis result, the cation-exchange membrane that known the present embodiment obtains, ion exchange capacity is higher, and the water content of film is suitable.This film dialysis flux and separation selectivity when the alkali DD, lower than embodiment 1 and 3, but still are better than business PPO film, illustrates that film passes through crosslinked with silicane and can effectively improve its application performance.
Claims (8)
1. a preparation method for diffusion dialysis cation-exchange membrane, is characterized in that: will contain two keys and-SO
3the monomer of Na group carries out electronics and shifts activating and regenerating catalyst atoms transferring free-radical polymerization, obtains polyelectrolyte; By even the aqueous solution blend of described polyelectrolyte and film matrix polyvinyl alcohol, then add silane coupler crosslinked, obtain coating liquid; By described coating liquid film, be then dried, heat treatment, obtain cation-exchange membrane.
2. preparation method according to claim 1, is characterized in that:
To contain two keys and-SO
3the monomer of Na group carries out electronics to be shifted activating and regenerating catalyst atoms transferring free-radical polymerization to obtain polyelectrolyte is to carry out as follows:
Step 1: in polymerization pipe, add solvent, by initator, catalyst, part and contain two keys and-SO
3the monomer of Na group is dissolved in described solvent, then in described polymerization pipe, passes into inert gas, bubbling 1-2h;
Step 2: reactant in polymerization pipe is refrigerated to solid-state, being then evacuated to vacuum in polymerization pipe is 0.05-100Pa, and keeps 2-5min, then pass into inert gas and return to normal pressure and keep 3min, finally reactant in polymerization pipe is thawed to liquid state;
Step 3: repeating step 2 twice again;
Step 4: add again reducing agent in polymerization pipe; and at polymerization pipe described in inert gas shielding lower seal, at 60-120 DEG C, stir polymerization 12-48h, stop polymerization; by product in polymerization pipe successively through precipitation, centrifugal, 60 DEG C be dried to constant weight, obtain polyelectrolyte.
3. preparation method according to claim 2, is characterized in that:
Described in step 1, solvent is the mixed solvent of dimethyl sulfoxide (DMSO) or the first alcohol and water formation that 1:1 mixes by volume; Described initator is selected from bromoethyl acetate, alpha-brominated ethyl butyrate or alpha-brominated different acetoacetic ester; Described catalyst is selected from copper bromide, copper chloride or iron chloride; Described part is selected from bipyridine, N, N, N', N', N " five methyl diethylentriamine or three-(N, N-dimethylaminoethyl) amine; Described contain two keys and-SO
3the monomer of Na group is SSS;
Described in step 4, reducing agent is selected from ascorbic acid, hydrazides or stannous octoate;
The mol ratio of described initator, catalyst, part and monomer is 20-50:1:50:200-800; The quality of described monomer and the volume ratio of described solvent are 1g:10-40ml; The mol ratio of described catalyst and described reducing agent is 1:5-10.
4. preparation method according to claim 2, is characterized in that:
Described inert gas is selected from argon gas, nitrogen or helium;
In step 2, reactant in polymerization pipe being refrigerated to solid-state is that reactant in polymerization pipe is cooled to below by liquid and is transformed into solid completely at-100 DEG C;
In step 2, reactant in polymerization pipe being thawed to liquid state is that polymerization pipe is placed at 10-40 DEG C, until reactant is liquid by solid-state thawing completely in polymerization pipe;
Described in step 4, stopping polymerization is that the polymerization pipe having sealed is broken, and reactant in polymerization pipe is exposed in air, and polymerization is stopped.
5. preparation method according to claim 2, is characterized in that:
Described in step 4, precipitation is that the product in polymerization pipe is added drop-wise in precipitating reagent and forms and precipitate; Described precipitating reagent is selected from oxolane or absolute ether.
6. preparation method according to claim 1, is characterized in that:
The mass ratio of described polyelectrolyte and described film matrix polyvinyl alcohol is 0.5-1.5:1; By the uniform step of aqueous solution blend of described polyelectrolyte and film matrix polyvinyl alcohol be: first prepare mass concentration and be the aqueous solution of 5% film matrix polyvinyl alcohol, then described polyelectrolyte at room temperature joined in the aqueous solution of described film matrix polyvinyl alcohol and stir 15-30min.
7. preparation method according to claim 1, is characterized in that:
The mass ratio of described polyelectrolyte and described silane coupler is 1:1-2.5; Described silane coupler is selected from γ-(2,3-epoxy the third oxygen) propyl trimethoxy silicane, tetraethoxysilane, (3-aminopropyl) triethoxysilane or γ-methacryloxypropyl trimethoxy silane; Described being cross-linked is at 25-60 DEG C of stirring reaction 20min-6h.
8. preparation method according to claim 1, is characterized in that:
Described film is that described coating liquid is coated on polyfluortetraethylene plate;
Described dry be by the polyfluortetraethylene plate that is coated with coating liquid be placed in circulation of air place until coating liquid exsiccation film forming film is taken off from tetrafluoroethene plate;
Described heat treatment is that the film of taking off from polyfluortetraethylene plate is first heated to 0.5-2h at 30-60 DEG C, then is warming up to 120-140 DEG C with the speed of 5-20 DEG C/h, and is incubated 2-5h.
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| CN106139926A (en) * | 2016-07-13 | 2016-11-23 | 合肥工业大学 | Polyelectrolyte composite membrane, its preparation method and the method for diffusion dialysis desalination |
| CN108654394A (en) * | 2018-05-29 | 2018-10-16 | 南京林业大学 | A kind of nanofiber cation-exchange membrane and the preparation method and application thereof |
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| CN106139926B (en) * | 2016-07-13 | 2019-03-22 | 合肥工业大学 | The method of polyelectrolyte composite membrane, preparation method and diffusion dialysis desalination |
| CN106139926A (en) * | 2016-07-13 | 2016-11-23 | 合肥工业大学 | Polyelectrolyte composite membrane, its preparation method and the method for diffusion dialysis desalination |
| CN108654394A (en) * | 2018-05-29 | 2018-10-16 | 南京林业大学 | A kind of nanofiber cation-exchange membrane and the preparation method and application thereof |
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