CN103261289B - Acid blocks anionic membrane - Google Patents
Acid blocks anionic membrane Download PDFInfo
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- CN103261289B CN103261289B CN201180061830.XA CN201180061830A CN103261289B CN 103261289 B CN103261289 B CN 103261289B CN 201180061830 A CN201180061830 A CN 201180061830A CN 103261289 B CN103261289 B CN 103261289B
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- 239000012528 membrane Substances 0.000 title claims abstract description 34
- 239000002253 acid Substances 0.000 title claims abstract description 23
- 125000000129 anionic group Chemical group 0.000 title description 10
- 150000001412 amines Chemical class 0.000 claims abstract description 34
- 239000004744 fabric Substances 0.000 claims abstract description 33
- 150000001450 anions Chemical class 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 18
- 238000004132 cross linking Methods 0.000 claims abstract description 14
- 238000009941 weaving Methods 0.000 claims abstract description 12
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 11
- 238000000909 electrodialysis Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- BZHJMEDXRYGGRV-UHFFFAOYSA-N vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 5
- 238000007598 dipping method Methods 0.000 claims abstract description 5
- 239000007870 radical polymerization initiator Substances 0.000 claims abstract description 4
- 230000002708 enhancing Effects 0.000 claims abstract description 3
- -1 unsaturated aliphatic tertiary amine Chemical class 0.000 claims description 20
- 150000003512 tertiary amines Chemical class 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 13
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 6
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-Vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 229920000728 polyester Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920002821 Modacrylic Polymers 0.000 claims description 2
- 125000001118 alkylidene group Chemical group 0.000 claims description 2
- 150000002978 peroxides Chemical class 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- MVVMETRGWFSULN-UHFFFAOYSA-N N',N',2-trimethyl-N-propylprop-2-enehydrazide Chemical compound CCCN(N(C)C)C(=O)C(C)=C MVVMETRGWFSULN-UHFFFAOYSA-N 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 229920001888 polyacrylic acid Polymers 0.000 claims 1
- 239000004584 polyacrylic acid Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 40
- 229920002799 BoPET Polymers 0.000 description 22
- 239000005041 Mylar™ Substances 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- 238000004806 packaging method and process Methods 0.000 description 15
- 239000011521 glass Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- FLCAEMBIQVZWIF-UHFFFAOYSA-N 6-(dimethylamino)-2-methylhex-2-enamide Chemical compound CN(C)CCCC=C(C)C(N)=O FLCAEMBIQVZWIF-UHFFFAOYSA-N 0.000 description 7
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 6
- 230000002522 swelling Effects 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 5
- 238000005352 clarification Methods 0.000 description 5
- VWDWKYIASSYTQR-UHFFFAOYSA-N Sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WERYXYBDKMZEQL-UHFFFAOYSA-N 1,4-Butanediol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- YYPNJNDODFVZLE-UHFFFAOYSA-M 3-methylbut-2-enoate Chemical compound CC(C)=CC([O-])=O YYPNJNDODFVZLE-UHFFFAOYSA-M 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N Methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 2
- 150000007516 brønsted-lowry acids Chemical class 0.000 description 2
- 150000007528 brønsted-lowry bases Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- BHBPJIPGXGQMTE-UHFFFAOYSA-N ethane-1,2-diol;2-methylprop-2-enoic acid Chemical compound OCCO.CC(=C)C(O)=O.CC(=C)C(O)=O BHBPJIPGXGQMTE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 101710031899 moon Proteins 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000003505 polymerization initiator Substances 0.000 description 2
- 235000010344 sodium nitrate Nutrition 0.000 description 2
- 239000004317 sodium nitrate Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- JROGBPMEKVAPEH-GXGBFOEMSA-N (2S,3R,11bS)-2-[[(1R)-6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolin-1-yl]methyl]-3-ethyl-9,10-dimethoxy-2,3,4,6,7,11b-hexahydro-1H-benzo[a]quinolizine;hydron;dichloride Chemical compound Cl.Cl.N1CCC2=CC(OC)=C(OC)C=C2[C@H]1C[C@H]1C[C@H]2C3=CC(OC)=C(OC)C=C3CCN2C[C@@H]1CC JROGBPMEKVAPEH-GXGBFOEMSA-N 0.000 description 1
- CYIGRWUIQAVBFG-UHFFFAOYSA-N 1,2-bis(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOCCOC=C CYIGRWUIQAVBFG-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- SSONCJTVDRSLNK-UHFFFAOYSA-L 2-methylprop-2-enoate;chloride Chemical compound [Cl-].CC(=C)C([O-])=O SSONCJTVDRSLNK-UHFFFAOYSA-L 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N 2-methylpropanenitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- FEPGCRWGNPMJMY-UHFFFAOYSA-N 3-amino-2-methyl-3-oxopropanoic acid Chemical compound NC(=O)C(C)C(O)=O FEPGCRWGNPMJMY-UHFFFAOYSA-N 0.000 description 1
- XRUKRHLZDVJJSX-UHFFFAOYSA-N 4-cyanopentanoic acid Chemical compound N#CC(C)CCC(O)=O XRUKRHLZDVJJSX-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N Di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Incidol Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- XFOZBWSTIQRFQW-UHFFFAOYSA-M benzyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC1=CC=CC=C1 XFOZBWSTIQRFQW-UHFFFAOYSA-M 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- AJCHRUXIDGEWDK-UHFFFAOYSA-N bis(ethenyl) butanedioate Chemical compound C=COC(=O)CCC(=O)OC=C AJCHRUXIDGEWDK-UHFFFAOYSA-N 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- VBWIZSYFQSOUFQ-UHFFFAOYSA-N cyclohexanecarbonitrile Chemical compound N#CC1CCCCC1 VBWIZSYFQSOUFQ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- FIKFOOMAUXPBJM-UHFFFAOYSA-N hepta-2,5-dienediamide Chemical compound NC(=O)C=CCC=CC(N)=O FIKFOOMAUXPBJM-UHFFFAOYSA-N 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- GNFWGDKKNWGGJY-UHFFFAOYSA-N propanimidamide Chemical compound CCC(N)=N GNFWGDKKNWGGJY-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TYFQFVWCELRYAO-UHFFFAOYSA-L suberate(2-) Chemical compound [O-]C(=O)CCCCCCC([O-])=O TYFQFVWCELRYAO-UHFFFAOYSA-L 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
Abstract
Provide the acid blocking-up anion selectivity polymeric membrane with weaving or non-weaving cloth enhancing structure type.The polymer of film is prepared by procedure below, and described process includes making component I, II and III copolymerization, and wherein I is ethylenically unsaturated aliphatic or aromatic uncle amine or quaternary amine monomer.II is cross-linking monomer, and III is vinyl chloride.Reaction is carried out in the presence of radical polymerization initiator.Furthermore disclosed the anion exchange membrane for electrodialysis plant type, and comprise the weaving with the copolymer dipping of the product comprising component I, II and III or non-weaving cloth.
Description
Invention field
The present invention relates to electrodialysis anion-selective membrane and the method producing such film.
Background of invention
Bipolar electrodialysis (BPED) is that membrane separating process, wherein high purity acid and aqueous slkali can be divided by electrodialytic water
Process (water splitting proces) is produced by saline solution.Generally, the equipment of design implementation such ED function is by position
The composition of the stacking containing multiple cation-selective membranes, bipolar membrane and anion-selective membrane between pair of electrodes.Heap
The folded assembly that can comprise cell compartment (unit cells) itself, the most each cell compartment includes above film, described film with
The mode of multiple flow path or passage is provided to arrange between adjacent film.
When DC current is applied to bipolar membrane, water splitting becomes OH-Ion and H+Ion, they migrate to respectively
Anode and negative electrode.Cation selective film easily makes cation (positively charged ion, such as Na+、H+) pass through, block simultaneously
Anion is passed through.On the contrary, anion-selective membrane easily allows anion (electronegative ion, such as Cl-、OH-) pass through,
Block cation transport simultaneously.If guiding saline solution (such as NaCl) by cation selective and anion-selective membrane
Between passage, the concentration of this saline solution by the adjacent passage containing bronsted lowry acids and bases bronsted lowry formed HCl and NaOH exhaust.
Be combined with some prior art ED devices, cross the H of anion selective membrane+Migration is proved problematic.By the moon
This proton seepage of ion selective membrane is it is well known that and referred to as Ge Luotusi mechanism (Grotthuss
Mechanism), the hydrogen bond network of hydrone is diffused through by this mechanism proton.Prove H+Essentially by or migrate the moon from
Sub-selective membrane is harmful for electrodialytic process, cause difference anion transfer current efficiency, the low concentration of bronsted lowry acids and bases bronsted lowry with
And high equipment and cost of energy.
Summary of the invention
In an exemplary embodiment, it is provided that a kind of have weaving for preparation or non-weaving cloth strengthens structure
The method that the acid of type blocks anion selectivity polymeric membrane.The polymer of film is prepared by procedure below, and described process includes
Make (I) ethylenically unsaturated aliphatic or aromatic uncle amine or quaternary amine monomer, (II) cross-linking monomer and (III) vinyl chloride
Component is copolymerization in the presence of radical polymerization initiator.In an exemplary embodiment, component (I): (II): (III's)
Mol ratio is about 20-60:30-70:1-19.In another exemplary embodiment, the mol ratio of component I:II:III is about
35-45:45-55:10-15.Preceding percentage sums to 100 moles of %.
In another aspect of this invention, copolymerization is carried out under there is not non-polymerisable solvent.
In another exemplary embodiment, the feature of film is that water content percentage ratio is about 12-20 weight %, and electricity
Stream efficiency is greater than about 93%.
In another aspect of this invention, it is provided that a kind of anion exchange membrane for electrodialysis plant type.Described film
Including weaving or non-weaving cloth, described cloth is immersed in the copolymer of the product comprising component I, II and III, and wherein I is
Ethylenically unsaturated aliphatic or aromatic uncle amine or quaternary amine monomer, II is cross-linking monomer, and III is vinyl chloride.
Detailed Description Of The Invention
In one aspect of the invention, acid blocks anion-selective membrane by by (I) ethylenically unsaturated aliphatic or aromatics uncle
Amine or quaternary amine monomer and (II) cross-linking monomer in the presence of (III) vinyl chloride (VBC) copolymerization and prepare.There is also certainly
By base polymerization initiator (IV).The most do not use solvent." acid blocks " used herein means the retardance H with enhancing+Migrate
The anion-selective membrane of the ability passed through.Generally, by reducing the water content of film and/or improving the crosslinking of polymer, it is achieved
This point.
Component I, II, III and initiator IV are mixed, to form homogeneous solution.Obtained solution is for dipping one piece
Cloth, such as polypropylene, polyester, acrylic acid or modacrylic type cloth.The cloth so impregnated is placed between glass plate,
And it is subsequently heated this glass sandwich structure, to cause polymerization.After completion of the polymerization reaction, glass sheet is removed, stays poly-
The cloth of compound dipping.
By being immersed in aqueous acidic bath (such as 2N HCl solution), make polymer impregnated cloth swelling subsequently.Polymerization
The cloth of thing dipping or sheet material can be used as acid in electrodialysis and other application subsequently and block anion-selective membrane.
About component I, exemplary aliphatic tertiary amine can include formula A.
Formula A-aliphatic tertiary amine
Wherein R1 is H or CH3, X is O or NH, and R2 is rudimentary (C1-C6) alkylidene, R3 and R4 is independently selected from rudimentary (C1-
C6) alkyl.
Exemplary compositions I aliphatic quaternary amine monomers can include formula B.
Formula B-aliphatic series quaternary amine
Wherein R1, R2, R3 and R4 such as formula A is defined；R5 is selected from rudimentary (C1-C6) alkyl；It is selected from halo, nitrous acid with A
Root.Sulfate radical and other inorganic or anion of organic anion.
Exemplary compositions I aromatic uncle amine monomer can include formula C.
Formula C-aromatic uncle amine
Wherein R6 is vinyl.
Exemplary compositions I aromatic quaternary ammonium monomer can include formula D.
Formula D
Wherein R6 is identical with formula C, and R2 is identical with formula A when it is present；R3, R4 are identical with formula B with R5, and A-With in formula B
Definition identical.
The concrete member of (I) ethylenically unsaturated aliphatic that can be mentioned that or aromatic uncle amine or quaternary amine monomer includes
I) trimethylaminoethyl group methacrylate chloride (TMAEMC)
Formula B-R1=CH3, R2=Et, R3, R4 and R5 are CH3, and A=Cl-；
Ii) vinylbenzyltrimethyl ammonium chloride (VBTMAC)
Formula D-R2=-CH2-, R3, R4 and R5=CH3, R6=vinyl, A=Cl-；
Iii) vinylpyridine
Formula C-R6=vinyl；
Iv) dimethyl amino ethyl methacrylate (DMAEMA)
Formula A-R1=CH3, X=O, R2=Et, R3 and R4=CH3；
V) dimethylaminopropyl Methacrylamide (DMAPMA)
Formula A-R1=CH3, X=NH, R2=propyl group, R3 and R4=CH3。
Cross-linking monomer II may be generally described as containing respect to olefinically unsaturated functional group and the known friendship of optional classification of comforting oneself
Connection agent, such as divinylbenzene (DVB), ethylene glycol dimethacrylate (EGDM), glycol diacrylate, 1,10-last of the ten Heavenly stems
Omega-diol diacrylate or dimethylacrylate, methylene-bisacrylamide or double Methacrylamide, ten dimethylenes pair
Acrylamide or double Methacrylamide, diglycol diacrylate or dimethylacrylate, 1,4-butanediol two
Vinyl ethers, triethylene-glycol divinyl ether, divinyl succinate, suberate (subernate) or decanedioic acid
Ester etc..
About spendable polymerization initiator, these include azo initiator, such as 2,2-azo double (2-methyl propionitrile),
Double (2-methyl-malonamic (the propionamidine)) dihydrochloride of 2,2'-azo；1,1'-azo is double (cyclohexanenitrile)；4,4'-
Double (4-cyanopentanoic acid) purum of azo etc., peroxide initiator, such as benzoyl peroxide and t-butyl peroxy-2-
Double (t-amyl peroxy) hexamethylene of ethylhexoate, 1,1-；Double (the t-butyl peroxy)-3,3,5-trimethyl-cyclohexane of 1,1-；1,
Double (t-butyl peroxy) hexamethylene of 1-；2,4-pentanedione peroxide；Double (the t-butyl peroxy)-2,5-dimethylhexane of 2,5-；
2-butanone peroxide；Two t-amyl peroxy compounds；Dicumyl peroxide；Lauroyl peroxide, t-butyl peroxy-2-
Ethylhexyl carbonate, t-butyl peracetate ester, tert-butyl peroxide and t-butyl peroxybenzoate etc..
In one embodiment, the addition scope of component (I), (II) and (III) is as follows: component I:II:III-(37-
40%): (48-50%): 12-13% mol ratio.
Embodiment
Embodiment 1 (A-1)
ABA-091509-vinylpyridine/DVB/VBC/PP 470
To 12 g (0.108 mol) 4-vinylpridine, 6 g (0.039 mol) vinyl chloride (VBC) and 24
The mixture of g (0.147 mol) 80% divinylbenzene (DVB) adds 0.8 g (1.9 weight %) t-butyl peroxy-2-second
Base alkyl caproate.Obtained solution is the solution of clarification, does not add any non-polymerisable solvent.Solution is poured into a size of
6.5 " in Mylar dish × 6.5 ", under Mylar dish, there is one block of glass, one block of mylar is placed in the solution, subsequently at cloth
On put one block of Mylar sheet material.Alternately cloth and Mylar sheet material, to form 3 layers of packaging, and places one piece of glass at the top of assembly
Glass.Keep mobile for packaging 2 hours to the baking oven of 90 DEG C of temperature subsequently.Packaging is taken apart, obtains 3 pieces of film sheet strengthened.
Film sheet is placed in 2 N hydrochloric acid solutions subsequently, makes it swelling, until balance.Final film is acid efficiency anionic membrane, its
Can be used for bipolar electrodialysis, for reclaiming mineral acid from salt.
Embodiment 2 (A-2)
ABA-092409 – DMAEMA/DVB/VBC/PP 447
To 10 g (.0604 mol) dimethyl amino ethyl methacrylate (DMAEMA), 3 g (.0189 mol)
The mixture of vinyl chloride (VBC) and 12 g (0.0735 mol) divinylbenzene (DVB) adds 0.5 g (2.0 weights
Amount %) t-butyl peroxy-2-ethylhexanoate.Obtained solution is the solution of clarification, does not add any non-polymerisable molten
Agent.Solution is poured into a size of 6.5 " × 6.5 " Mylar dish in, under Mylar dish, have one block of glass, by one piece of polypropylene (#
477) cloth is placed in the solution.Subsequently, one block Mylar sheet material is placed above at cloth.An another piece of cloth and Mylar sheet material are placed on
In solution.Cloth and Mylar sheet material alternate intervals, to form 3 layers of packaging, and place one block of glass at the top of assembly.Subsequently
Packaging is moved to baking oven and keeps 2 hours at a temperature of 90 DEG C.Packaging is taken apart, obtains 3 pieces of film sheet strengthened.Subsequently will
Film sheet is placed in 2N HCl solution, makes it swelling, until balance.Final film is acid efficiency anionic membrane, and it can be used for
Bipolar electrodialysis, for reclaiming mineral acid from salt.
Embodiment 3 (A-3)
ABA-100609 – DMAEMA/DVB/VBC/PE
To 60 g (0.363 mol) dimethyl amino ethyl methacrylate (DMAEMA), 18 g (0.114 mol)
The mixture of vinyl chloride (VBC) and 72 g (0.442 mol) 80% divinylbenzene (DVB) adds 3 g (2 weights
Amount %) t-butyl peroxy-2-ethylhexanoate.Obtained solution is the solution of clarification, does not add any non-polymerisable molten
Agent.Solution is poured into a size of 10 " x11 " Mylar dish in, under Mylar dish, have one block of glass；One block of mylar is placed
In the solution, on cloth, one block of Mylar sheet material is put subsequently.Alternately place cloth and Mylar sheet material, to form 3 layers of packaging, and
One block of glass is placed at the top of assembly.Move to packaging subsequently the baking oven of 90 DEG C of temperature keeps 2 hours.Packaging is taken apart,
To 3 pieces of film sheet strengthened.Film sheet is placed in 2 N hydrochloric acid solutions subsequently, makes it swelling, until balance.Final film
For acid efficiency anionic membrane, it can be used for bipolar electrodialysis, for reclaiming mineral acid from salt.
Embodiment 4
Above film and other commercially available films some is used to carry out film compartment test (Membrane cell
testing).Method described in embodiment 2 by United States Patent (USP) 4,822,471 measures membrane current efficiency.Current efficiency hundred
Proportion by subtraction refers to that the electric current transmission anion using given percentage passes through anionic membrane.The electric current of residue percentage ratio represents that hydrogen oozes
Anionic membrane is passed through in leakage.Mark " by force " alkali refers to quarternary amine functional group, and " weak " alkali represents tertiary amine functional group.By by film at 2N
NaCl solution is soaked, first film is converted into Cl-(chloride) form, be washed out going on a tour from Cl-Ion, measures in film
Quaternary amine.Subsequently, another kind of salt (such as sodium nitrate solution) is used for Cl-Ion exchanges from film, and titrates Cl-.Cause
This can calculate the electric capacity of the quaternary amine in film, in terms of meq/ every g dried resin.In order to measure the tertiary amine in film, measure total amine and (include season
Amine and tertiary amine).Subsequently the amount of quaternary amine is deducted from the total amine amount existed.In order to determine that the total amine being present in film (includes season
Amine and tertiary amine), first tertiary amine is converted into salt by adding HCl.(quaternary amine also can be converted into Cl by this-Form).Subsequently, use
100% ethanol solution washes out the HCl of excess.Sodium nitrate solution is used to be swapped out Cl subsequently-Ion, and titrate Cl-Ion.Subsequently
The total amount of amine can be calculated.Obtain following result and be shown in Table I.
Table I
The C-3-poly-(vinylpyridine) radioactivity grafting in fluorinated copolymer；It is available from Solvay-Solvay ARA
* Journal of Membrane Science, the data of 326 (2009) 650-658 are derived from.
The C-4-poly-(vinylpyridine) radioactivity grafting in fluorinated copolymer；It is available from Solvay-Solvay AW
* derives from Journal of Membrane Science, the data of 110 (1996) 181-190.
C-5-vinylpyridine/DVD/ polychloroethylene film；It is available from Asahi Glass.
Embodiment 5
(092509-470)
To 46 g (0.257 mol) dimethylaminopropyl Methacrylamide (DMAPMA), 12.8 g (0.084
Mol) mixture of vinyl chloride (VBC) and 48 g (0.295 mol) 80% divinylbenzene (DVB) adds 2.1 g
(2 weight %) t-butyl peroxy-2-ethylhexanoate.Obtained solution is the solution of clarification, does not add any non-polymerizable
Solvent.Solution is poured into a size of 10 " × 11 " Mylar dish in, under Mylar dish, have one block of glass, by one block of polypropylene
Cloth is placed in the solution, puts one block of Mylar sheet material subsequently on cloth.Alternately place cloth and Mylar sheet material, to form 3 layers of packaging,
And one block of glass is placed at the top of assembly.Move to packaging subsequently the baking oven of 90 DEG C of temperature keeps 2 hours.Packaging is torn open
Open, obtain 3 pieces of film sheet strengthened.Film sheet is placed in 2 N hydrochloric acid solutions subsequently, makes it swelling, until balance.Finally
Film be acid efficiency anionic membrane, it can be used for bipolar electrodialysis, for reclaiming mineral acid from salt.
Comparative example: (C-6) (ABA-#082809 VP/DVB/PP 470)
To 15 g (0.136 mol) 4-vinylpridine and 30 g (0.184 mol) 80% divinylbenzene (DVB)
Mixture in add 0.8 g (1.9 weight %) t-butyl peroxy-2-ethylhexanoate.Vinyl chloride (VBC) is not added
Enter in solution.Obtained solution is the solution of clarification, does not add any non-polymerisable solvent.Pour solution into size
Be 6.5 " × 6.5 " Mylar dish in, one piece of polypropylene cloth is placed in the solution, on cloth, puts one block of Mylar sheet material subsequently.
Alternately place cloth and Mylar sheet material, to form 3 layers of packaging, and place one block of glass at the top of assembly.Subsequently packaging is moved
Keep 2 hours to the baking oven of 90 DEG C of temperature.Packaging is taken apart, obtains 3 pieces of film sheet strengthened.Subsequently film sheet is placed on
In 2 N hydrochloric acid solutions, make it swelling, until it reaches balance.Final film is acid efficiency anionic membrane.The character of film is set forth in down
Table II:
Table II
* resistance is under 1000 Hz, measures in 0.01N NaCl solution.
Film A-1 contains quaternary amine (highly basic) tertiary amine (weak base), and the height owing to VBC and tertiary amine (vinylpyridine) react
But crosslinking, causes having compared with low water content, higher current efficiency low-resistance film.It is (weak that comparative film (C-6) contains only tertiary amine
Alkali), cause low water content and high current efficiency but the film of much higher resistance.
Embodiment 6 (program similar with the embodiment 2 of United States Patent (USP) 4,822,471)
Use three compartment electrodialysis test compartments to measure the current efficiency (C.E.) of the film of the present invention, be used for as with working as
The contrast of those prior aries of acid solution.Compartment comprises negative electrode and the anode electrode of the platinum being coated with titanium, and they are positioned at the end of compartment
End, between be located two films, and the spacer being disposed and used liner each other disposes with electrode, with formed containing liquid every
Room.Therefore, arrangement is as follows: anion exchange membrane to be tested, intermediate compartment, commercially available types of cationic exchange membrane (GE
CR61CMP), anodal compartment, be finally anode electrode.
The film being arranged in test compartment has 25 cm2Active membrane, and the liquid volume of each compartment respectively be about 40
Ml, and cross section active area is 25 cm2.Solution in compartment comprises 1 N HCl in cathodic compartment, and 0.5 N HCl exists
In central compartment, and 0.5N H2SO4In the anode compartment.By using magnetic stirrer solution and being maintained at the temperature of 25 DEG C
Under degree.Each test is at 20 mA/cm220 minute stage of lower operation, now by the acid concentration in titration determination compartment.Result
It is shown in lower Table III:
Table III
Obviously, by adding VBC in the mixture of vinylpyridine/DVB or DMAEMA/DVB or DMAPMA/DVB, mixed
Compound is homogenizing.It is therefore not necessary to solvent is used for being polymerized.Upon polymerization, VBC also with a part of reactive tertiary amine, cause that there is season
The film of both amine and tertiary amine, with high crosslinking degree.The A-3 film tested as shown in Table III presents the highest (93%) and higher
Acid current efficiency.
By adding VBC with anti-with a part of tertiary amine in monomer (such as vinylpyridine, DMAEMA, DMAPMA etc.)
Should, we can be controlled in quaternary amine and the ratio of tertiary amine in obtained film, the most also can improve film crosslinking.Due to obtained film
High crosslinking degree and low water content, high current efficiency can be obtained by aliphatic monomers (such as DMAEMA, DMAPMA etc.).Due to
Introducing quaternary amine in film, resistance also reduces.
At a preferred aspect of the present invention, it is I that anion blocks anion-selective membrane) DMAEMC, II (DVB)
Polymeric reaction product with III (VBC).The mol ratio of I:II:III can be about 20-60:30-70:1-19, more preferably 37-
45:45-55:10-15.Preferably initiator is t-butyl peroxy-2-ethylhexanoate.More particularly, this reaction is shown in formula E
The following reaction process of display, obtained polymer is shown in formula F.
Formula E-reaction process
Polymer obtained by formula F-
The acid of the present invention blocks the water content that is further characterized by of anionic membrane and is about 12-20%, preferably from about 13-18%.
Additionally, they present current efficiency is about 93% and bigger, and the about 20-70% that quarternary amine functional group be total amine based on existence,
The most specifically in the range of about 30-40%, as proved by specific embodiments illustrated herein.
It should be understood that the embodiments described herein is exemplary only, and without departing from claims
Under the spirit and scope of the present invention limited, those skilled in the art can carry out many and change and modifications.
Claims (20)
1. for preparation, there is weaving or non-weaving cloth strengthens the method that the acid of structure blocks anion selectivity polymeric membrane, described
The polymer of film is prepared by procedure below, in the presence of described process is included in radical polymerization initiator, makes component (I) olefinic
Unsaturated aliphatic or aromatic uncle amine monomer, (II) cross-linking monomer and (III) vinyl chloride copolymerization, described polymer have with
The tertiary amine of meq/ every g dried resin meter 1.27: 0.9～1.52: 0.53 scope and the ratio of quaternary amine, and described film have 93% and
Above current efficiency.
2. the method for claim 1, wherein component I: the mol ratio of II: III is 20-60: 30-70: 1-19, Qi Zhongsuo
State I, II and III and sum to 100 moles of %.
3. method as claimed in claim 2, wherein component I: the mol ratio of II: III is 35-45: 45-55: 10-15.
4. the method for claim 1, described copolymerization is carried out under there is not non-polymerisable solvent.
5. the method for claim 1, wherein said component (I) includes ethylenically unsaturated aliphatic tertiary amine.
6. the method for claim 1, wherein said component (I) includes olefinic unsaturation aromatic uncle amine.
7. method as claimed in claim 5, wherein said component I includes the member selected from DMAEMA and DMAPMA.
8. method as claimed in claim 6, wherein said component I is vinylpyridine.
9. method as claimed in claim 7, wherein said radical polymerization initiator includes peroxide initiator.
10. method as claimed in claim 7, wherein said cross-linking monomer includes the member selected from DVB and EGDM.
11. methods as claimed in claim 10, wherein said cloth includes selected from polypropylene woven cloths, Polyester woven cloth and poly-third
The member of olefin(e) acid woven cloths, the water content % of described film is 12-20 weight %, and 1, under 000Hz, molten at 0.01N NaCl
The resistance Rohm-cm measured in liquid2For 50-100.
12. methods as claimed in claim 10, wherein said cloth includes selected from polypropylene woven cloths, Polyester woven cloth, polyester
Woven cloths, polyacrylic acid woven cloths and the member of modacrylic woven cloths.
13. 1 kinds of anion exchange membrane for electrodialysis plant type, described film comprises weaving or non-weaving cloth, and described cloth is used
Comprising the copolymer dipping of the product of component (I), (II) and (III), wherein (I) is ethylenically unsaturated aliphatic or aromatics uncle
Amine monomers, (II) is cross-linking monomer, and (III) is vinyl chloride, and described polymer has in terms of meq/ every g dried resin
The tertiary amine of 1.27: 0.9～1.52: 0.53 scopes and the ratio of quaternary amine, and described film has 93% and above current efficiency.
14. anion exchange membrane as claimed in claim 13, wherein said component (I) is selected from formula A and C, wherein
Formula A-aliphatic tertiary amine
Wherein R1 is H or CH3, X is O or NH2, R2 is low alkyl group (C1-C6) alkylidene, and R3 and R4 is independently selected from rudimentary
(C1-C6) alkyl；
Formula C-aromatic uncle amine
Wherein R6 is vinyl.
15. anion exchange membrane as claimed in claim 14, wherein component I: the mol ratio of II: III is 20-60: 30-70:
1-19%, wherein preceding percentage is added and reaches 100%.
16. anion exchange membrane as claimed in claim 15, wherein component I: the mol ratio of II: III is 35-45: 45-55%
: 10-15%.
17. anion exchange membrane as claimed in claim 15, wherein component I: the mol ratio of II: III is 37-40%: 48-
50%: 12-13%.
18. anion exchange membrane as claimed in claim 16, wherein said component (I) includes selected from DMAEMA's and DMAPMA
Member, the feature of described film is that current efficiency is more than 93%.
19. anion exchange membrane as claimed in claim 18, wherein crosslinking monomer component (II) is becoming selected from DVB with EGDM
Member.
The anion exchange membrane of 20. 1 kinds of fabrics comprising enhancing by polymer, described polymer has a structure that
Wherein in terms of meq/ every g dried resin (m-1): the ratio of 1 is in 1.27: 0.9～1.52: 0.53 scopes.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US12/977923 | 2010-12-23 | ||
| US12/977,923 US8470896B2 (en) | 2010-12-23 | 2010-12-23 | Acid block anion membrane |
| US12/977,923 | 2010-12-23 | ||
| PCT/US2011/065312 WO2012087770A1 (en) | 2010-12-23 | 2011-12-16 | Acid block anion membrane |
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| Publication Number | Publication Date |
|---|---|
| CN103261289A CN103261289A (en) | 2013-08-21 |
| CN103261289B true CN103261289B (en) | 2016-11-30 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896271A (en) * | 2007-12-18 | 2010-11-24 | 通用电气公司 | Anion exchange polymers, methods for making and materials prepared therefrom |
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101896271A (en) * | 2007-12-18 | 2010-11-24 | 通用电气公司 | Anion exchange polymers, methods for making and materials prepared therefrom |
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