JPH0585575B2 - - Google Patents
Info
- Publication number
- JPH0585575B2 JPH0585575B2 JP5934586A JP5934586A JPH0585575B2 JP H0585575 B2 JPH0585575 B2 JP H0585575B2 JP 5934586 A JP5934586 A JP 5934586A JP 5934586 A JP5934586 A JP 5934586A JP H0585575 B2 JPH0585575 B2 JP H0585575B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- group
- fluorine
- ion exchange
- membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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- 239000003014 ion exchange membrane Substances 0.000 claims description 40
- 239000012528 membrane Substances 0.000 claims description 35
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 25
- 229910052731 fluorine Inorganic materials 0.000 claims description 25
- 239000011737 fluorine Substances 0.000 claims description 25
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 12
- 238000005341 cation exchange Methods 0.000 claims description 11
- 238000005349 anion exchange Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 5
- 125000000542 sulfonic acid group Chemical group 0.000 claims description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 25
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 18
- -1 hydroxide ions Chemical class 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 17
- 239000002904 solvent Substances 0.000 description 13
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 12
- 239000000126 substance Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 229920001577 copolymer Polymers 0.000 description 8
- 150000004985 diamines Chemical class 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000001412 amines Chemical class 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- 229940100198 alkylating agent Drugs 0.000 description 6
- 239000002168 alkylating agent Substances 0.000 description 6
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 6
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 4
- 239000002585 base Substances 0.000 description 4
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 description 3
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 229910015900 BF3 Inorganic materials 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 230000002152 alkylating effect Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- OBRMNDMBJQTZHV-UHFFFAOYSA-N cresol red Chemical compound C1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(C)C(O)=CC=2)=C1 OBRMNDMBJQTZHV-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 125000005265 dialkylamine group Chemical group 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- FIMAYKDZLLQUDW-UHFFFAOYSA-N fluoro(dioxido)borane;trimethyloxidanium Chemical compound C[O+](C)C.C[O+](C)C.[O-]B([O-])F FIMAYKDZLLQUDW-UHFFFAOYSA-N 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 229940102396 methyl bromide Drugs 0.000 description 3
- OIRDBPQYVWXNSJ-UHFFFAOYSA-N methyl trifluoromethansulfonate Chemical compound COS(=O)(=O)C(F)(F)F OIRDBPQYVWXNSJ-UHFFFAOYSA-N 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012280 lithium aluminium hydride Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- HVOYZOQVDYHUPF-UHFFFAOYSA-N n,n',n'-trimethylethane-1,2-diamine Chemical compound CNCCN(C)C HVOYZOQVDYHUPF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 2
- 238000010186 staining Methods 0.000 description 2
- 229940124530 sulfonamide Drugs 0.000 description 2
- 150000003456 sulfonamides Chemical class 0.000 description 2
- 150000008054 sulfonate salts Chemical class 0.000 description 2
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 description 1
- QLEIDMAURCRVCX-UHFFFAOYSA-N 1-propylpiperazine Chemical compound CCCN1CCNCC1 QLEIDMAURCRVCX-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- IUNMPGNGSSIWFP-UHFFFAOYSA-N dimethylaminopropylamine Chemical compound CN(C)CCCN IUNMPGNGSSIWFP-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- QOHMWDJIBGVPIF-UHFFFAOYSA-N n',n'-diethylpropane-1,3-diamine Chemical compound CCN(CC)CCCN QOHMWDJIBGVPIF-UHFFFAOYSA-N 0.000 description 1
- DILRJUIACXKSQE-UHFFFAOYSA-N n',n'-dimethylethane-1,2-diamine Chemical compound CN(C)CCN DILRJUIACXKSQE-UHFFFAOYSA-N 0.000 description 1
- SORARJZLMNRBAQ-UHFFFAOYSA-N n,n',n'-trimethylpropane-1,3-diamine Chemical compound CNCCCN(C)C SORARJZLMNRBAQ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000005956 quaternization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000565 sulfonamide group Chemical group 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Manufacture Of Macromolecular Shaped Articles (AREA)
Description
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[Field of the Invention] The present invention relates to a novel fluorine-containing three-layer ion exchange membrane. More specifically, the present invention relates to a fluorine-containing three-layer ion exchange membrane having a three-layer structure, with cation exchange groups in both layers and an anion exchange group in the center layer. The fluorine-containing three-layer ion exchange membrane of the present invention can be used as a battery separator, a selective membrane for monovalent and multivalent ions, and the like. [Prior Art] Conventionally, hydrocarbon polymers have been used as such multilayer ion exchange membranes. As these methods, a method has been proposed in which the surface of the ion exchange membrane is treated with a polymer electrolyte, or a method in which both sides are impregnated with a monomer and polymerized. However, problems such as membrane destruction due to repeated drying and swelling and improvements in chemical resistance have not been solved. [Problems to be Solved by the Invention] The present invention solves the above problems. [Means for Solving the Problems] The present inventors have conducted intensive studies on a membrane that will not be destroyed by repeated drying and swelling and has chemical resistance, especially oxidation resistance. structure, the pendant chains on both sides have cation exchange groups, the pendant chains in the middle layer have cation exchange groups, the pendant chains in the middle layer have anion exchange groups, and the main chain is A non-crosslinked fluorine-containing ion exchange membrane made of a perfluorocarbon polymer was discovered and the present invention was completed. In the three-layer membrane of the present invention, preferably the cation exchange group is a sulfonic acid group and the anion exchange group is a quaternary ammonium group. More preferably, in the three-layer ion exchange membrane of the present invention, the layer having a cation exchange group in the pendant chain has the following general formula:
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éã«ã¢ããªã³äº€æåºãæããå±€ãäžè¬åŒ[Chemical formula ] q is a positive number and its ratio p/q is 2-16. The layer consisting of repeating units represented by the general formula
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ããªæ§é ã®éåäœãäŸç€ºããããšãã§ããã[Image Omitted] This is a fluorine-containing three-layer ion exchange membrane consisting of repeating units where x, l, m, n, p and q are the same as above, and z is a group containing a quaternary ammonium group. In both formulas, l, m and n can take different numbers for each pendant chain even on the same main chain. Furthermore, the value of p/q means an average value in the copolymer, and it goes without saying that the value of p/q includes cases in which each repeating unit takes a different value. Specifically, the layered cation exchange groups forming the layers on both sides of the three-layer structure ion exchange membrane of the present invention can be exemplified by polymers having the following structures.
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åäœãäŸç€ºããããšãã§ãããembedded image The counter ion of these cation exchange groups may be a hydrogen ion or an alkali metal ion such as a sodium ion or a potassium ion. Specifically, the layered anion exchange group forming the central layer of the three-layer structure ion exchange membrane of the present invention can be exemplified by a polymer having the following group as Z in the above general formula. .
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ãã[Image Omitted] Examples of counter ions for these anion exchange groups include hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodine ions; and trifluoromethanesulfonate ions. The thickness of the layered cation exchange groups and layered anion exchange groups of the present invention is preferably from about 1 ÎŒm to about 1 ÎŒm.
It is in the range of 200ÎŒm. The fluorine-containing three-layer ion exchange membrane of the present invention may be in the form of a flat membrane or a tube. The fluorine-containing three-layer ion exchange membrane of the present invention is
For example, it can be produced using a copolymer film composed of repeating units represented by the following general formula as a raw material.
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have the same meanings as above. l, m and n can take different numbers for each pendant chain even on the same main chain, and the value of p/q means the average value in the copolymer, and takes different values for individual repeating units. The same applies to cases. in particular,
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äžã®éãã§ãããembedded image The thickness of the copolymer film used as a raw material is preferably in the range of about 10 ÎŒm to about 500 ÎŒm.
The exchange group concentration can range from 0.3 meq/g dry resin to 1.2 meq/g dry resin. As for the shape, it is preferable to use a flat membrane or a tube-shaped membrane depending on the shape of the intended fluorine-containing three-layer ion exchange membrane of the present invention. The fluorine-containing three-layer ion exchange membrane of the present invention is
It can be obtained by introducing a quaternary ammonium group into the central layer of such a raw material copolymer film by chemical modification, for example, using the following route. Route 1 This route passes through a homogeneous sulfonic acid film, passes through a three-layer film with sulfonic acid on both sides and carboxylic acid in the center, and converts the carboxylic acid layer into a layer containing quaternary ammonium groups. A system three-layer structure ion exchange membrane is obtained. The exchange of terminal groups is shown below using a chemical formula containing only the terminal groups.
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äžã®éãã§ããã[Formula] R 5 = lower alkyl group, substituted or unsubstituted phenyl group, or lower perfluoroalkyl group, Q = the same as above. Route 1 will be explained below. The three-layer membrane of sulfonic acid/carboxylic acid/sulfonic acid used as a raw material membrane in this route is, for example, made by converting homogeneous sulfonic acid into sulfonyl chloride,
It can be obtained by hydrolyzing both sides so that a sulfonyl chloride group remains in the center, introducing sulfonic acid on both sides, and further carboxylating the sulfonyl chloride group present in the center (Example 1
reference). The carboxylic acid layer of the resulting three-layer film is converted into a carboxylic ester by reacting with an alcohol in the presence of an acid or by reacting with an orthoformic acid ester. Next, after drying this membrane, it is converted into a carboxylic acid amide by reacting it with a lower dialkylamine represented by the following general formula HNR 1 R 2 (1). Examples of the lower dialkylamine represented by the above general formula (1) include dimethylamine, diethylamine,
Examples include dipropylamine, methylethylamine, pyrrolidone, and piperidine. The reaction with these amines can be carried out by bringing the gaseous amine into contact with the membrane, in a liquid amine, or using a solvent. In this case, ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and dioxane, and hydrocarbons such as benzene, toluene, and hexane can be used as the solvent. Note that the same carboxylic acid amide can also be similarly obtained by reacting a lower dialkylamine represented by the general formula (1) with the corresponding carboxylic acid chloride. The carboxylic acid amide thus obtained is
It can be converted into an amine by the action of a reducing agent. As the reducing agent, lithium aluminum hydride, diborane, etc. can be used, but diborane is superior in terms of reaction efficiency. The diborane used can be generated by, for example, reacting a boron trifluoride ether complex with sodium borohydride, or various complexes of borane (such as dimethyl sulfide complex) can be used. The reaction proceeds smoothly in an ether solvent such as tetrahydrofuran, dioxane, or diethylene glycol dimethyl ether. In addition, in the early stage of the reaction, the temperature is kept in the range of ice-cold temperature to room temperature, and then,
Heating to reflux temperature to 100°C is preferred in order to complete the reaction. The obtained amine can be converted into the fluorine-containing three-layer structure ion exchange membrane of the present invention by alkylating (quaternizing) it with an alkylating agent (R 3 D). Examples of the alkylating agent include methyl iodide, methyl bromide, n-propyl bromide, trimethyloxonium fluoroborate ((CH 3 ) 3 OBF 4 ),
Triethyloxonium fluoroborate ((C 2
H 5 ) 3 OBF 4 ), trimethyloxonium hexachloroantimonate ((CH 3 ) 3 OSbCl 6 ), methyl trifluoromethanesulfonate, etc. can be used. At this time, methanol, ethanol, methylene chloride, chloroform, carbon tetrachloride, etc. may be used as a solvent. If it is necessary to exchange the counter ion of the above-obtained fluorine-containing three-layer ion exchange membrane, this can be done by treating it with an alkali metal salt by a conventional method. Route 2 This route passes from a homogeneous sulfonic acid membrane to a sulfonic acid/carboxylic acid/sulfonic acid trilayer membrane.
A fluorine-containing three-layer ion exchange membrane is obtained by converting the carboxylic acid layer into a layer containing a quaternary ammonium group. The conversion of the terminal group is shown below using the chemical formula of only the terminal group.
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Converts to aminocarboxylic acid amide. As the diamine represented by the above general formula (2),
N,N-dimethylethylenediamine, N,N,
N'-trimethylethylenediamine, N,N-dimethyltrimethylenediamine, N,N,N'-trimethyltrimethylenediamine, N-methylpiperazine, N,N-diethyltrimethylenediamine, N-ethylpiperazine and N-propylpiperazine etc. can be exemplified. At this time, a corresponding silylamine in which the hydrogen atom on the nitrogen atom in the above general formula (2) is replaced with a trimethylsilyl group can also be used in place of the above diamine. Further, the reaction with these diamines can be carried out in a liquid amine or using a solvent. At this time, as a solvent, diethyl ether,
Ethers such as tetrahydrofuran and dioxane, hydrocarbons such as benzene, toluene, hexane, etc. can be used. As the reducing agent, lithium aluminum hydride, diborane, etc. can be used, but diborane is superior in terms of reaction efficiency. The diborane used can be generated by, for example, reacting a boron trifluoride ether complex with sodium borohydride, or various complexes of borane (dimethyl sulfide complex, etc.) can be used. The reaction proceeds smoothly in an ether solvent such as tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, or the like. In addition, in the initial stage of the reaction, it is preferable to maintain the temperature between ice-cooling temperature and room temperature, and then to heat the temperature between the reflux temperature and 100° C. in order to complete the reaction. By alkylating the obtained diamine with an alkylating agent, it can be converted into a fluorine-containing three-layer ion exchange membrane. Examples of the alkylating agent include methyl iodide, methyl bromide, n-propyl bromide, trimethyloxonium fluoroborate ((CH 3 ) 3 OBF 4 ),
Triethyloxonium fluoroborate ((C 2
H 5 ) 3 OBF 4 ), trimethyloxonium hexachloroantimonate ((CH 3 ) 3 OSbCl 6 ), methyl trifluoromethanesulfonate, etc. can be used. At this time, methanol, ethanol, methylene chloride, chloroform, carbon tetrachloride, etc. may be used as a solvent. If it is necessary to exchange the counter ion of the above-obtained fluorine-containing three-layer ion exchange membrane, it can be carried out by treatment with an alkali metal salt by a conventional method. Route 3 This route involves hydrolyzing both sides of the homogeneous sulfonyl fluoride membrane to introduce a sulfonic acid so that a sulfonyl fluoride group remains in the center, then reacting the central sulfonyl fluoride group with a diamine, and then forming a quaternary fluoride membrane. By this process, a fluorine-containing three-layer ion exchange membrane is obtained. The conversion of the terminal group is shown below using the chemical formula of only the terminal group.
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å®æœäŸ ïŒ[Chemical formula] (R 3 , R 6 , R 7 , R 8 , D, a and Z are the same as above) Route 3 will be explained below. The synthesis of a membrane with a sulfonamide group in the center is
This is achieved by reacting a diamine represented by the general formula (2) or the corresponding silylamine described above with a membrane having sulfonic acid on both sides and a sulfonyl fluoride group in the center. At this time, it is preferable to use a large excess of diamines or to coexist a tertiary amine. A solvent can be used in the reaction, such as diethyl ether (ether), ethers such as tetrahydrofuran, benzene, toluene,
Hydrocarbons such as hexane can be used. The reaction is usually carried out at a temperature ranging from 0°C to 150°C. The resulting sulfonamide membrane can be converted into a fluorine-containing three-layer ion exchange membrane by alkylating it with an alkylating agent. Examples of the alkylating agent include methyl iodide, methyl bromide, n-propyl bromide, trimethyloxonium fluoroborate (Me 3 OBF 4 ), triethyloxonium fluoroborate (Et 3
OBF 4 ), trimethyloxonium hexachloroantimonate (Me 3 OSbCl 6 ), methyl trifluoromethanesulfonate, and the like can be used.
At this time, methanol, ethanol, methylene chloride, chloroform, carbon tetrachloride, etc. may be used as a solvent. If it is necessary to exchange the counter ion of the fluorine-containing three-layer ion exchange membrane obtained here, it can be carried out by treatment with an alkali metal salt by a conventional method. The fluorine-containing three-layer ion exchange membrane of the present invention is
Although some of the pendant chains contain hydrocarbon groups, it surprisingly shows extremely good durability under harsh oxidizing atmospheres such as chlorine atmospheres. In particular, it is a non-crosslinked type, withstands repeated drying and swelling, does not peel off, and has excellent chemical resistance and solvent resistance. Therefore, when used, for example, as a diaphragm for batteries or a membrane for separating monovalent and multivalent ions, it not only has remarkable durability, but also resists drying and swelling, which has traditionally been considered impossible. It exhibits extremely excellent performance when applied to associated equipment, used in systems containing solvents, and used under oxidizing conditions. Yet another major advantage is that it can be handled dry. This is an important point when used on an industrial scale. [Example] Next, a method for evaluating the obtained film in Examples will be described. 1 Repeated drying-swelling...Study item A After processing in methanol at 65°C for 48 hours, the moisture content is measured using a membrane in which the process of removing the solvent under vacuum at 40°C is repeated 5 times. 2. Peeling condition...Consideration item B Judgment is made by taking a cross-sectional photograph of the film in 1 above. 3 Chemical resistance...Study item C Measure the water content and exchange capacity (NMR and titration method, quantification of S) of the membrane into which Cl 2 gas was introduced at 10 to 40 ml/min for 50 hours at 60°C in water. Example 1
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g. Dry film) and then hydrolyzed. next
After treatment with 2N HCl and thorough washing with water, heat at 60°C.
and dried under vacuum. Next, this membrane was treated with a mixed solution of phosphorus pentachloride and phosphorus oxychloride to form a sulfonyl chloride. Next, the mixture was hydrolyzed with 10 wt caustic soda/methanol (1/1; volume ratio) at room temperature so that sulfonic acid was formed in a layer of about 10 ÎŒm, and then washed with water. Then, oxidation treatment was performed to carboxylate the remaining sulfonyl chloride layer. The carboxylic acid layer of the sulfonic acid/carboxylic acid/sulfonic acid film thus obtained was esterified with methanol-HCl. The membrane obtained above was immersed in dry ether, dimethylamine gas was passed through it under ice cooling, and the mixture was reacted for 6 hours under cooling and for 18 hours at room temperature. 80â with 1.5% sodium bicarbonate water-methanol mixed solution.
Washed for 5 hours and dried under reduced pressure overnight. A colorless and transparent film was obtained, and in the surface infrared spectrum of the layer removed by about 12 to 15 microns from the surface, CH absorption was observed at 2930 and 1420 cm -1 and absorption due to amide carbonyl was observed at 1700 cm -1 . Next, sodium borohydride was dissolved in dry diethylene glycol dimethyl ether under an argon atmosphere, and then the membrane obtained above was immersed. A dry diglyme solution of boron trifluoride ether complex was added dropwise to the solution under ice cooling. By reacting under cooling for 5 hours and then at 100°C for 18 hours,
The absorption at 1700 cm -1 in the infrared spectrum disappeared, indicating that reduction to the amine layer had completely progressed. After washing the obtained membrane with methanol, it was placed in a methanol solution of methyl iodide and reacted at 60°C for 80 hours. After washing the obtained membrane with methanol,
The reaction was carried out in a methanol solution of lithium chloride at 60°C for 24 hours. This film was heated to 60°C in methanol to obtain a film having the desired quaternary ammonium chloride layer. In a dyeing test, the resulting three-layer ion exchange membrane was colored reddish-purple (basic aqueous solution) or yellow-orange (methanol solution) in the central thickness of about 180 Όm with cresol red, indicating that quaternary ammonium groups were present. It was shown that it was formed in the central layer. The three-layer ion exchange membrane obtained as described above was treated and evaluated according to the evaluation method described above. The evaluation results are shown below. Meanwhile, the approximately 10Ό layer on both sides was colored blue with crystal violet. From the above results, it was found that the obtained membrane was a three-layer ion exchange membrane containing a sulfonate salt in a layer of about 10 Όm on both sides and a quaternary ammonium salt in a layer of about 185 Όm in the center.
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g. Dry film). So that the sulfonic acid is formed in a layer of about 10Ό
After hydrolyzing with 10 wt% caustic soda/methanol (1/1; volume ratio) at room temperature, it was washed with water. N-methylpiperazine was reacted in the resulting dry ether. Thereafter, it was washed with warm water and dried. In the surface infrared spectrum of the layer removed by about 12 to 15 Ό from the surface, 2930 cm -1 , 2850 cm -1 , 1450 to 1430
Absorption due to C-H was observed at cm -1 . The resulting membrane was reacted with methyl iodide in methanol at 50°C for 48 hours. It was then washed in methanol and treated with a methanol solution of lithium chloride for 24 hours. It was further washed in methanol at 50°C for 8 hours. In the infrared spectrum of the film after drying, the absorption in the 3000 to 2800 cm 1 region of the sulfonamide layer was shifted to the higher wavenumber side due to quaternization. As a result of a cresol red staining test, the resulting three-layer ion exchange membrane was colored reddish-purple at a thickness of approximately 130 Όm in the center, indicating that quaternary ammonium groups were formed in the center layer. Meanwhile, on both sides approx.
The 10Ό layer was colored blue with crystal violet. From the above results, the obtained membrane has approximately
It was found to be a three-layer ion exchange membrane containing a sulfonate salt in the 5Ό layer and a quaternary ammonium salt in the central approximately 130Ό layer. The exchange capacity was 0.9 meq/g dry membrane for the sulfonic acid base layer and 0.7 meq/g dry membrane for the quaternary ammonium base layer. Evaluation of this three-layer structure ion exchange membrane was carried out in Example 1.
showed similar results. Example 3 A reaction was carried out in the same manner as in Example 2 except that N,N,N'-trimethylethylenediamine was used in place of the N-methylpiperazine used in Example 2 to obtain a three-layer structure ion exchange membrane. The exchange capacity was 0.9 meq/g dry membrane for the sulfonic acid base layer and 0.7 meq/g dry membrane for the quaternary ammonium base layer. Evaluation of this three-layer ion exchange membrane showed the same results as in Example 1. Example 4
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0.92 meq/g dry resin). Next 10wt
% caustic soda/methanol and from both sides.
Hydrolyzed to a depth of 7Ό. Using this tube, a reaction was carried out in the same manner as in Example 3. In a staining test, the approximately 110Ό central layer was colored reddish-purple with cresol red, and the presence of quaternary ammonium chloride groups was confirmed in the approximately 110Ό central layer. Meanwhile, the approximately 7Ό layer on both sides was colored blue with crystal violet. From the above results, it can be seen that the obtained membrane is a three-layer ion exchange membrane containing a sulfonate in the approximately 7 Όm layer on both sides and a quaternary ammonium salt in the approximately 110 Όm layer in the center. The resulting three-layer ion exchange tube had an exchange capacity of 0.92 meq/g dry resin for the sulfonic acid layer and 0.84 meq/g dry resin for the quaternary ammonium chloride layer. The obtained three-layer structure ion exchange tube was evaluated in the same manner as in Example 1 and showed the same results.
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Figure 1 shows the surface infrared absorption spectrum of the layer containing the quaternary ammonium group of the three-layer structure film obtained in Example 1, and Figure 2 shows the spectrum of the three-layer structure film obtained in Example 1. .
Claims (1)
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èã[Claims] 1. Has a three-layer structure, has a cation exchange group in the pendant chains of both layers, has an anion exchange group in the pendant chain of the central layer, and has a main chain made of a perfluorocarbon polymer. Non-crosslinked fluorine-containing three-layer ion exchange membrane. 2. The fluorine-containing three-layer ion exchange membrane according to claim 1, wherein the cation exchange group is a sulfonic acid group and the anion exchange group is a quaternary ammonium group. 3 The layer having a cation exchange group on the pendant chain has the following general formula: or 1, n=1 or an integer from 2 to 5, p and q are positive numbers, and the ratio p/q is from 2 to 16. A layer consisting of repeating units represented by the following and having an anion exchange group in the pendant chain has the general formula: x, l, m, n, p and q are the same as above, z is a group containing a quaternary ammonium group The fluorine-containing three-layer structure ion exchange membrane according to claim 1, which comprises the repeating unit represented by the above formula. 4 Claims 1, 2, or 3 in which the fluorine-containing three-layer ion exchange membrane is in the form of a flat membrane.
The fluorine-containing three-layer structure ion-exchange membrane described in 2. 5. The fluorine-containing three-layer ion exchange membrane according to claim 1, 2 or 3, wherein the fluorine-containing three-layer ion exchange membrane is tube-shaped.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5934586A JPS62218424A (en) | 1986-03-19 | 1986-03-19 | Fluorine-containing ion exchange membrane having three-layered structure |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP5934586A JPS62218424A (en) | 1986-03-19 | 1986-03-19 | Fluorine-containing ion exchange membrane having three-layered structure |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS62218424A JPS62218424A (en) | 1987-09-25 |
JPH0585575B2 true JPH0585575B2 (en) | 1993-12-08 |
Family
ID=13110613
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP5934586A Granted JPS62218424A (en) | 1986-03-19 | 1986-03-19 | Fluorine-containing ion exchange membrane having three-layered structure |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS62218424A (en) |
-
1986
- 1986-03-19 JP JP5934586A patent/JPS62218424A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS62218424A (en) | 1987-09-25 |
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