KR20030016253A - 폴리머 막 - Google Patents
폴리머 막 Download PDFInfo
- Publication number
- KR20030016253A KR20030016253A KR1020027014744A KR20027014744A KR20030016253A KR 20030016253 A KR20030016253 A KR 20030016253A KR 1020027014744 A KR1020027014744 A KR 1020027014744A KR 20027014744 A KR20027014744 A KR 20027014744A KR 20030016253 A KR20030016253 A KR 20030016253A
- Authority
- KR
- South Korea
- Prior art keywords
- metal
- membrane
- film
- elemental
- polymer
- Prior art date
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- 229920005597 polymer membrane Polymers 0.000 title 1
- 239000012528 membrane Substances 0.000 claims abstract description 52
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 9
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000002378 acidificating effect Effects 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 5
- 125000000467 secondary amino group Chemical group [H]N([*:1])[*:2] 0.000 claims abstract description 5
- 125000001302 tertiary amino group Chemical group 0.000 claims abstract description 5
- 150000003852 triazoles Chemical class 0.000 claims abstract description 5
- 150000007513 acids Chemical class 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 3
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract 5
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 6
- 150000004703 alkoxides Chemical class 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 125000003453 indazolyl group Chemical group N1N=C(C2=C1C=CC=C2)* 0.000 claims description 4
- -1 polydiphenylphenylene Polymers 0.000 claims description 4
- 229920002530 polyetherether ketone Polymers 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- 150000004027 organic amino compounds Chemical class 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 4
- 150000001412 amines Chemical class 0.000 claims 3
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 2
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 239000010409 thin film Substances 0.000 claims 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 229910019142 PO4 Inorganic materials 0.000 claims 1
- 239000004734 Polyphenylene sulfide Substances 0.000 claims 1
- 229920000491 Polyphenylsulfone Polymers 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000000010 aprotic solvent Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims 1
- 229910001863 barium hydroxide Inorganic materials 0.000 claims 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 239000012964 benzotriazole Substances 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 150000001768 cations Chemical class 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000000502 dialysis Methods 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- 238000002848 electrochemical method Methods 0.000 claims 1
- 238000000909 electrodialysis Methods 0.000 claims 1
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000005267 main chain polymer Substances 0.000 claims 1
- 229910001463 metal phosphate Inorganic materials 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 238000005373 pervaporation Methods 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 229920001643 poly(ether ketone) Polymers 0.000 claims 1
- 229920002492 poly(sulfone) Polymers 0.000 claims 1
- 229920005649 polyetherethersulfone Polymers 0.000 claims 1
- 229920001955 polyphenylene ether Polymers 0.000 claims 1
- 229920000069 polyphenylene sulfide Polymers 0.000 claims 1
- 238000001223 reverse osmosis Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 239000000758 substrate Substances 0.000 claims 1
- 210000002268 wool Anatomy 0.000 claims 1
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 5
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 150000001556 benzimidazoles Chemical class 0.000 abstract description 3
- 150000001565 benzotriazoles Chemical class 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 150000004679 hydroxides Chemical class 0.000 abstract description 3
- 150000002460 imidazoles Chemical class 0.000 abstract description 3
- 150000003217 pyrazoles Chemical class 0.000 abstract description 3
- 125000005605 benzo group Chemical group 0.000 abstract 1
- 229940049706 benzodiazepine Drugs 0.000 abstract 1
- 125000003226 pyrazolyl group Chemical group 0.000 abstract 1
- 238000012958 reprocessing Methods 0.000 abstract 1
- 239000010936 titanium Substances 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- 229920000554 ionomer Polymers 0.000 description 9
- 229920000557 Nafion® Polymers 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 5
- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000004693 Polybenzimidazole Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229920001490 poly(butyl methacrylate) polymer Polymers 0.000 description 3
- 229920002480 polybenzimidazole Polymers 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 239000004697 Polyetherimide Substances 0.000 description 2
- 229920003182 Surlyn® Polymers 0.000 description 2
- 239000005035 Surlyn® Substances 0.000 description 2
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 2
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229920003936 perfluorinated ionomer Polymers 0.000 description 1
- 229920000075 poly(4-vinylpyridine) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- JNMRHUJNCSQMMB-UHFFFAOYSA-N sulfathiazole Chemical compound C1=CC(N)=CC=C1S(=O)(=O)NC1=NC=CS1 JNMRHUJNCSQMMB-UHFFFAOYSA-N 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
- B01D67/00933—Chemical modification by addition of a layer chemically bonded to the membrane
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
- B01D67/00111—Polymer pretreatment in the casting solutions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0048—Inorganic membrane manufacture by sol-gel transition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/1411—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix
- B01D69/14111—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes containing dispersed material in a continuous matrix with nanoscale dispersed material, e.g. nanoparticles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2275—Heterogeneous membranes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
본 발명은 다음의 조성을 갖는 신규한 유기/무기 하이브리드 막이다:
-SO3H, -PO3H2, -COOH 또는 B(OH)2그룹을 함유하는 폴리머산;
측쇄(side chain) 또는 주쇄(main chain)의 어느 한 쪽에 제1차, 제2차 또는 제3차 아미노 그룹, 피리딘 그룹, 이미다졸, 벤즈이미다졸, 트리아졸, 벤조트리아졸, 피라졸 또는 벤조피라졸 그룹을 함유하는 폴리머염기(선택적);
상기 언급한 염기성 그룹을 함유하는 추가 폴리머염기(선택적);
막 형성 공정동안, 원소 유기화합물 및/또는 금속 유기화합물의 가수분해 및/또는 졸-겔 반응 및/또는 산성, 알칼리 또는 중성의 수성 전해질에서의 막의 재처리에 의해 얻어진 원소옥시드 또는 원소히드록시드 또는 금속 옥시드 또는 금속 히드록시드.
또한, 본 발명은 상기 막의 제조방법 및 상기 타입의 막의 다양한 용도에 관한 것이다.
Description
이오노머(ionomer)/무기 하이브리드 복합체에 관한 선행기술은 유기폴리머,특히 나피온(Nafion)®(Organic-inorganic hybrid materials: perfluorinated ionomers as sol-gel polymerization templates for inorganic alkoxides K.A.Mauritz Mat. Sci. Eng. C6 (1998) 121-133)과 같은 이오노머 분야에서의 졸/겔 기술 수행의 선구자 중 하나인 Mauritz의 개설에 공지되어 있다. 상기 공정의 핵심은 이온적으로 기능화된 유기폴리머의 매트릭스안에서 원소유기 또는 금속유기 화합물의 원소 또는 금속 옥시드 또는 히드록시드 네트워크로의 가수분해이다.
상기 문건에 기술된 시스템의 실시예는 다음과 같다.
(a) 나피온®을 물 및 알코올에서 미리 부풀리고 난 후 테트라에톡시실란(TEOS)/알코올 용액에 담근다. 나피온막의 클러스터(cluster)와 그 후의 졸-겔 반응이 술폰산안에서 술폰산 양성자 촉매에 의하여 TEOS로부터 물을 함유하는 SiO2/OH 네트워크로 발생한다("나노복합체")(Microstructural evolution of a Silicon Oxide Phase in a Perfluorosulfonic Acid ionomer by an In Situ Sol-Gel Reaction, K.A.Mauritz, I. D. Stefanithis, S.V.Davis, et al. J. Appl. Polym. Sci. 55, 181-190(1995)).
(b) 나피온®을 물 및 알코올에서 미리 부풀리고 난 후, Zr(OBu)4의 알코올 용액에 담근다. 나피온막의 클러스터와 그 후의 졸-겔 반응이 술폰산안에서 술폰산 양성자 촉매에 의하여 Zr(OBu)4로부터 물을 함유하는 ZrO2네트워크로 발생한다("나노복합체")(Asymmetric Nafion/(Zirconium Oxide)Hybrid Membranes via In Situ Sol-Gel Chemistry, W.Apichatachutapan, R. B. Moore, K. A.Mauritz, J. Appl.Polym.Sci.62, 417-426(1996)).
(c) 나피온 술포닐 플루오리드(nafion sulfonyl fluoride)전구체 막은 퍼플루오로히드로페난트렌(perfluorohydrophenanthrene)에서 미리 부풀리고 난 후, 3-아미노프로필트리에톡시실란(3-aminopropyltriethoxysilane)에 담근다. 그 후, 잔여 실란은 에탄올로 세정한다. 하이브리가 생성되고, 여기에서, 폴리머와 부분적으로 가교된 SiO2-네트워크가 상기 실란의 가수분해 및 상기 실란과 SO2F-그룹과의 반응에 의하여 막 매트릭스안에 형성된다(Chemical modification of a nafion sulfonyl fluoride precursor via in situ sol-gel reactions, A. J. Greso, R. B. Moore, K. M. Cable, W. L. Jarrett, K. A. Mauritz, Polymer 38, 1345-1356(1997).
(d) Zn2+형태의 서린(Surlyn)®이오노머 막은 1-프로판올에서 부풀리고 난 후, H2O/TEOS 혼합물에 담근다. 그 후 졸-겔 반응이 술폰산 양성자 촉매에 의하여 막 매트릭스안에서 TEOS로부터 물을 함유하는 SiO2/OH네트워크로 발생한다("나노복합체")(Surlyn®/[Silicon Oxide] Hybrid Materials. 2. Physical Properties Characterization, D. A. Siuzdak, K. A. Mauritz, J. Polym. Sci. Part B: Polymer Physics, 37, 143-154(1999)).
공지 시스템 (a) 내지 (d)의 불이익은 졸-겔 반응이 이미 형성된 막에서 발생하고, 그 결과, 가수분해에 의하여 형성된 무기 폴리머상 및 폴리머 복합체의 함량을 임의로 조절할 수 없다는 것이다.
또한 비이온폴리머 및 금속 또는 원소 옥시드의 하이브리드 시스템이 상기 문건에 기술되어 있다:
(e) 폴리(n-부틸메타아크릴레이트)폴리머 용액의 알코올 용액에 가해진 티타늄 알콕시드의, 용매 증발후, 폴리머 매트릭스안에서의 수증기 가수분해에 의해 만들어진 폴리(n-부틸메타아크릴레이트) 및 티타늄옥시드의 복합체.(Novel Poly(n-Butyl Methacrylate)/Titanium Oxide Alloys Produced by the Sol-Gel process for Titanium Alkoxides, K. A. Mauritz, C. K. Jones, J. Appl. Poly. Sci. 40, 1401-1420(1990)).
(f) 0.15M의 HCl 용액을 가하여 NMP에서의 폴리에테르이미드 Ultem®의 용액의 TEOS의 가수분해에 의하여 만들어진 폴리에테르이미드 및 나노분산된 실리시움옥시드(silicium oxide)의 복합체막. 가수분해후 밀집되거나 상역전된 막이 상기 폴리머용액으로부터 만들어진다. 무기상과 유기상간의 융합성(compatibility)은 3-아미노프로필트리메톡시실란(AS)를 별도로 추가함으로서 얻는다(Membranes of poly(ether imide) and nanodispersed silica, S. P. Nunes, K. V. Peinemann, K, Ohlrogge, A. Alpers, M. Keller, A. T. N. Pires, J. Memb. Sci. 157(1999)219-226)).
상기 시스템들은 앞서 기술한 바와 같은 유사한 불리한 점들을 나타낸다.
기술한 내용에서 보여주듯이, 이미 다수의 순수 유기 양성자 전도막 및 무기 첨가제가 구비된 양성자전도막이 개시되어 있지만, 상기 시스템 모두는 열안정성 및 기계적 안정성이 좋지 않고, 이는 특히 100℃온도 이상 부분에 충격을 준다.
본 발명은 다음의 조성을 갖는 신규한 유기/무기 하이브리드 막에 관한 것이다:
ㆍ-SO3H, -PO3H2, -COOH 또는 B(OH)2그룹을 함유하는 폴리머산
ㆍ측쇄(side chain) 또는 주쇄(main chain)의 어느 한 쪽에 제1차, 제2차, 또는 제3차 아미노 그룹, 피리딘 그룹, 이미다졸, 벤즈이미다졸, 트리아졸, 벤조트리아졸, 피라졸 또는 벤조피라졸 그룹을 함유하는 폴리머 염기(선택적).
ㆍ상기 언급한 염기 그룹을 함유하는 추가적인 폴리머 염기(선택적).
ㆍ막 형성중에 원소유기(elementorganic) 및/또는 금속유기(metalorganic) 화합물의 가수분해 및/또는 졸-겔 반응, 및/또는 수성의 산성, 알칼리성 또는 중성 전해질에서의 막의 후처리에 의해 얻어진 원소(element) 또는 금속(metal) 옥시드(oxide) 또는 히드록시드(hydroxide).
본 발명은 또한 상기 막의 제조방법 및 이러한 타입의 막의 다양한 용도에 관한 것이다.
따라서, 본 발명의 목적은 추가로 무기 원소/금속 옥시드/히드록시드 상을 함유하는 양이온 교환 폴리머 및 염기성 폴리머의 혼합물의 신규한 복합체 또는 복합체막을 제공하는 것이고, 이는 다음과 같은 막 성질을 개선한다:
ㆍ기계적 안정성
ㆍ열안정성
ㆍ100℃ 초과 온도에서의 물 보유 능력의 개선, 이는 특히, 100℃초과 온도 범위에서의 막 연료 전지에서의 적용에 특히 중요하다.
상기 목적은 제 1 항의 막을 제공함으로서 해결된다.
또한, 본 발명의 방법은 상기 목적을 해결하는데 기여한다.
여기에서, 원소/금속 옥시드/히드록시드의 유기전구체는 폴리머 용액(알콕시드/에스테르, 아세틸아세토네이트 등)안으로 첨가된다.
이오노머안에서의 무기상의 형성은 막 형성후, 산성, 알칼리성 및/또는 중성의 수성 분위기에서, 가수분해에 의해 발생한다.
놀랍게도, Ti 디아세틸아세토네이트 디이소프로필레이트/이소프로판올을 염형태의 술폰화된 폴리(에테르에테르케톤) sPEEK 및 NMP 또는 DMAc안의 염기성 폴리머(예를 들어, 폴리벤즈이미다졸 PBI 세라졸(Celazol)®)의 용액안으로 첨가하면, Ti 디아세틸아세토네이트 디이소프로필레이트는 폴리머 용액안에서 가수분해하지 않고, 용매 증발시에 막 매트릭스를 형성하는 것을 발견하였다. 놀랍게도, 유기 Ti 화합물은 수성 잿물 및/또는 물 및/또는 산에서 졸/겔 반응을 통한 막의 연속적후처리에 의하여 막 매트릭스안에서 나노분산된 티타늄 옥시드로 가수분해된다는 것을 발견하였다. 막 매트릭스내의 상기 티타늄 옥시드는 EDX에 의하여 확인할 수 있다. 따라서, 막 매트릭스내의 TiO2의 함량은 35중량% 까지 이를수 있다.
본 발명의 복합체는 다음과 같이 구성되어 있고,
ㆍ -SO3H, -PO3H2, -COOH 또는 B(OH)2그룹을 갖는 폴리머산
바람직하게는 알릴 주쇄 폴리머 뼈대(polymer backbone)를 가진다.
ㆍ (선택적으로) 측쇄 또는 주쇄의 어느 한 쪽에 제1차, 제2차 또는 제3차 아미노 그룹, 피리딘 그룹, 이미다졸, 벤즈이미다졸, 트리아졸, 벤조트리아졸, 피라졸 또는 벤조피라졸 그룹을 가지는 하나 또는 두개의 폴리머염기
ㆍ 다음의 원소유기 및/또는 금속유기 화합물의 클래스의 가수분해에 의하여 얻어진 원소 또는 금속 옥시드 또는 히드록시드:
ㆍ Ti, Zr, Sn, Si, B, Al의 금속/원소 알콕시드/에스테르
ㆍ 금속 아세틸아세토네이트, 예를 들어, Ti(acac)4, Zr(acac)4
ㆍ 금속/원소 알콕시드 및 금속 아세틸아세토네이트의 혼합 화합물, 예를 들어 Ti(acac)2(OiPr)2등
ㆍ Ti, Zr, Sn, Si, B, Al의 유기 아미노 화합물
막 형성 공정 중 및/또는 수성의 산성, 알칼리성 또는 중성 전해질에서의 막의 후처리에 의하여 생성가능하다.
나노분산된 무기상이 본 발명의 막 매트릭스안으로 추가되기 때문에 본 발명의 이오노머(혼합체)막의 특성 프로파일은 크게 개선된다.
본 발명의 신규한 무기/유기 하이브리드 산 염기 혼합막은 뛰어난 특성 프로파일을 나타낸다:
ㆍ 좋은 양성자 전도도
ㆍ 뛰어난 열안정성
ㆍ 뛰어난 기계적 안정성
ㆍ 제한된 팽창(swelling)
특히 T>100℃에서 수분 보유 능력이 크게 개선된다. 이는 막안에서 나노분산된 무기 성분의 분포를 보여주는 무기 옥시드/히드록시드에 의해 달성된다. 몇몇 공개문서(Comparison of Ethanol and Methanol Oxidation in a Liquid-Feed Solid Polymer Electrolyte Fuel Cell at High Temperature A.S. Arico, P. Creti, P. L. Antonucci, V. Antonucci, Electrochem. Sol.St.Lett.182)66-68)(1998))에서 이미 제안된 바와 같이 옥시드 분말을 이오노머막 안으로 혼합시키는 것으로는 원소유기/금속유기 화합물이 막 매트릭스내에서만 옥시드로 가수분해되는 본 발명의 방법에서와 같은 막 매트릭스안에서의 매우 균일한 무기 구성성분 분포를 얻을 수 없다. 따라서, 본 발명의 막은 다음과 같은 이점을 더욱 나타낸다.
ㆍ 감소된 메탄올 투과도
ㆍ 특히 T>100℃에서 양성자 전도도에의 기여
본 발명은 다음의 실시예에 의해 상술된다.
이오노머 혼합막 TJ-3의 제조
2g의 술폰화 폴리에테르 에테르 케톤 빅트렉스(Victrex)®(이온 교환 능력 1.364 meq SO3H/g)을 10g의 N-메틸피롤리디논에 용해시켰다. 그 후, 1g의 트리에틸아민을 상기 용액에 가하여 sPEEK의 술폰산 그룹을 중화시켰다. 그 후, 77mg의 폴리(4-비닐피리딘)을 상기 용액에 가하였다. 용해시킨후, 5.1g의 티타늄(Ⅳ)비스(아세틸아세톤아토)디이소프로필레이트, 이소프로판올에서 75중량%의 용액을 상기 용액에 가하였다. 그 후, 폴리머 용액 필름을 디가스(degass)한 후, 닥터나이프(doctor knife)로 글래스-플레이트상에 800㎛ 두께 필름으로 캐스트(cast)하였다. 막 건조기안에서, 100℃에서, 상기 용매를 제거하였다. 필름 건조후, 폴리머 필름이 있는 글래스-플레이트를 H2O와 함께 물통안에 담갔다. 글래스-플레이트로부터 필름을 벗겨냈다. 상기 필름을 1N NaOH에서, 70℃에서, 24시간동안, 그 후, 탈이온화물(deionized water)에서, 70℃에서, 24시간동안 후처리 하였다. 그 후, 상기 필름을 탈이온화물안에서 상온에서 저장하였다. 양성자 전도도를 측정하기 위해서 상기 필름을 0.5N H2SO4안에서, 상온에서 24시간 동안 평형시켰다.
특성 결과 ;
필름 두께[㎛];100
IEC[meq SO3H/g];1.15
팽창[%]:104
선택투과도(permselectivity)(0.5N/0.1N NaCl)[%]:78.35
Rsp H+(0.5 N HCl)[Ωcm]:6.4
Rsp H+(H2O)[Ωcm]:16.9
Rsp Na+(0.5 N NaCl)[Ωcm]:29.6
도 1에 TJ3막의 EDX 스펙트럼을 나타내었다. Ti 신호가 명확히 나타났다.
이오노머 혼합막 JOA-2의 제조
3g의 술폰화 폴리(에테르에테르케톤) 빅트렉스®(이온 교환 능력 1.75 meq SO3H/g)을 15g의 N-메틸피롤리디논에 용해시켰다. 그 후, 0.5g의 n-폴리아민을 상기 용액에 가하여 sPEEK의 술폰산 그룹을 중화시켰다. 그 후, 0.15g의 폴리머 1(도 2)을 상기 용액에 가하였다. 그 후, 10.72중량%의 PBI Celazol®(도 3) 1.4g 을 상기 용액에 가하였다. 그 후, 4.036g의 티타늄(Ⅳ)비스(아세틸아세톤아토)디이소프로필레이트, 이소프로판올에서 75중량% 용액을 상기 용액에 가하였다. 그 후, 상기 폴리머 용액 필름을 디가스한 후, 닥터나이프로 글래스-플레이트상에 800㎛ 두께 필름으로 캐스트 하였다. 진공 건조 오븐안에서 용매를, 먼저 75℃ 및 800mbar에서 1시간동안 제거하고, 120℃에서 먼저 800mbar로, 그 후, 50mbar로 낮추어 제거하였다. 필름 건조후, 폴리머 필름이 있는 글래스-플레이트를 H2O와 함께 물통안에 담갔다. 글래스-플레이트로부터 필름을 벗겨냈다. 상기 필름을 1N NaOH에서 70℃에서 24시간동안, 그 후, 탈이온화물에서 70℃에서 24시간동안 후처리 하였다. 그 후, 상기 필름을 탈이온화물안에서 상온에서 저장하였다. 양성자 전도도를 측정하기 위해서 상기 필름을 0.5N H2SO4안에서, 상온에서 24시간 동안 평형시켰다.
특성 결과 ;
필름 두께[㎛];100
IEC[meq SO3H/g];0.97
팽창[%]:27.7
선택투과도[%]:94.9
Rsp H+(0.5N H2SO4)[Ωcm]:21.8
Rsp H+(H2O)[Ωcm]:55.6
Rsp Na+(0.5N NaCl)[Ωcm]:79
도 4에 JOA-2막의 EDX 스펙트럼을 나타내었다. Ti 신호가 명확히 나타났다.
Claims (15)
- 막 형성 공정 전, 중, 후에 염, 금속옥시드 또는 금속히드록시드 또는 이들의 유기 전구체가 막안으로 혼입되는 것을 특징으로 하는 적어도 하나의 폴리머산을 함유하는 막.
- 제 1 항에 있어서, 막 형성 공정 중 또는 후에 염, 금속옥시드 또는 금속히드록시드 또는 이들의 유기 전구체가 막안으로 혼입되는 것을 특징으로 하는 적어도 하나의 폴리머산 및 적어도 하나의 폴리머염기를 함유하는 막.
- 제 1 항에 있어서, 상기 폴리머산은 알릴 주쇄(aryl main chain)폴리머이고, 산성 그룹으로서 SO3H-, PO3H2, COOH 또는 B(OH)2또는 이들의 염을 포함하고, 폴리에테르술폰, 폴리술폰, 폴리페닐술폰, 폴리에테르에테르 술폰, 폴리에테르 케톤, 폴리에테르 에테르 케톤, 폴리페닐렌 에테르, 폴리디페닐페닐렌 에테르, 폴리페닐렌 설피드의 그룹으로부터 선택되고 또는 코폴리머이고, 상기 구성성분 중 적어도 하나를 함유하는 것을 특징으로 하는 막.
- 제 1 항에 있어서, 상기 폴리머염기는 측쇄(side chain) 또는 주쇄의 어느 한 쪽에 제1차, 제2차 또는 제3차 아미노그룹, 피리딘그룹, 이미다졸, 벤즈이미다졸, 트리아졸, 벤조트리아졸, 피라졸 또는 벤조피라졸 그룹을 함유하는 것을 특징으로 하는 막.
- 제 1 항 내지 제 4 항 중 어느 한 항에 있어서, 상기 막은 막 형성 전, 중 또는 후에 가수분해 및/또는 졸/겔 반응에 의해 얻어진 염, 원소옥시드(elemental oxide) 또는 원소히드록시드(elemental hydroxide) 또는 금속옥시드 또는 금속히드록시드를 포함하고, 다음의 전구체:Ti, Zr, Sn, Si, B, Al의 금속/원소 알콕시드/에스테르금속 아세틸아세토네이트, 예를 들어 Ti(acac)4, Zr(acac)4금속/원소 알콕시드 및 금속 아세틸아세토네이트의 혼합 화합물, 예를 들어 Ti(acac)2(OiPr)2등Ti, Zr, Sn, Si, B, Al의 유기 아미노 화합물로부터 선택되는 것을 특징으로 하는 막.
- 제 1 항 내지 제 5 항 중 어느 한 항에 있어서, 상기 막은 추가적으로 공유 가교(covalently cross-linked)되는 것을 특징으로 하는 막.
- 제 1 항 내지 제 6 항 중 어느 한 항에 있어서, 상기 막은 인산(phosphoric acid)으로 후처리되어 막 매트릭스내에서 금속옥시드 및/또는 금속히드록시드 및/또는 금속옥시드히드록시드로부터, 양성자 전도도에 기여하는 금속 인산염(metal phosphate) 또는 원소 인산염(element phosphate) 또는 금속 수소인산염(metal hydrogenphosphate) 또는 원소 수소인산염(elemental hydrogenphosphate) 또는 금속 이수소인산염 또는 원소 이수소인산염을 생성하는 것을 특징으로 하는 막.
- 다음의 성분:SO3X, PO3X2, COOX, 또는 B(OX)2(X = H, 1가 또는 2가 또는 3가 또는 4가 금속양이온)을 가지는 폴리머산,측쇄 및/또는 주쇄의 어느 한 쪽에 제1차, 제2차 또는 제3차 아미노그룹, 피리딘그룹, 이미다졸, 벤즈이미다졸, 트리아졸, 벤조트리아졸, 피라졸 또는 벤조피라졸그룹을 가지는 적어도 하나의 폴리머염기 및제4항 기재의 적어도 하나의 금속유기 또는 원소유기 화합물들이 N-메틸피롤리디논(NMP), N,N-디메틸아세트아미드(DMAc), N,N-디메틸포름아미드(DMF), 디메틸설폭시드(DMSO) 또는 술포란(sulfolane)과 같은 이중극성-아프로틱(dipolar-aprotic)용매안에서 혼합되는 것을 특징으로 하는 제 1 항 내지 제 7 항 중 어느 한 항 기재의 복합체(composites) 및 복합체막(composite membranes)의 제조 방법.
- 제 8 항에 있어서, 제 7 항 기재의 폴리머 용액이 지지체(유리-플레이트 또는 금속 플레이트, 티슈, 직물(woven), 비직물, 양모(fleece), 다공성(폴리머)막)상에 박막으로 캐스트되고, 상기 용매는 80℃ 내지 150℃의 온도에서, 정상 압력에서, 또는 진공하에서 증발되고, 형성된 박막은 다음과 같이 후처리되고,(1) T = 50 내지 100℃에서, 물안에서(2) T = 50 내지 100℃에서, 1 내지 100% 미네랄산(히드로칼산(hydrokalic acid), 황산, 인산)안에서(3) 1 내지 50%의 수성염기(예를 들어, 암모니아 용액, 아민 용액, 수산화나트륨 용액, 수산화칼륨 용액, 탄산나트륨 용액, 수산화칼슘 용액, 수산화바륨 용액)안에서, 또는 무수 액체 아민 또는 상이한 액체아민 혼합물안에서(4) T = 50 내지 100℃에서, 물안에서여기에서, 상기 후처리단계의 순서는 변화될 수 있고, 또한 선택적으로 단계(1) 및/또는 (2) 및/또는 (3)이 생략될 수 있는 것을 특징으로 하는 제조방법.
- 전기화학적 방법에 의해 에너지를 생산하는데 사용되는 제 1 항 기재 막의 용도.
- 0 내지 180℃의 온도에서 막 연료 전지(H2또는 직접 메탄올 연료 전지)의 구성성분으로 사용되는 제 1 항 기재 막의 용도.
- 전기 화학 전지에 사용되는 제 1 항 기재 막의 용도.
- 2 차 배터리에 사용되는 제 1 항 기재 막의 용도.
- 전기 분해 전지에 사용되는 제 1 항 기재 막의 용도.
- 가스분리(gas separation), 투석증발(pervaporation), 퍼스트랙션(perstraktion), 역삼투(reverse osmosis), 전기투석(electrodialysis) 및 확산투석(diffusion dialysis)에 사용되는 제 1 항 기재 막의 용도.
Applications Claiming Priority (3)
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DE10021106A DE10021106A1 (de) | 2000-05-02 | 2000-05-02 | Polymere Membranen |
DE10021106.2 | 2000-05-02 | ||
PCT/DE2001/000624 WO2001061908A1 (de) | 2000-02-18 | 2001-02-16 | Verfahren, kommunikationssystem und empfänger zum übertragen von daten in paketform |
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KR20030016253A true KR20030016253A (ko) | 2003-02-26 |
KR100845295B1 KR100845295B1 (ko) | 2008-07-09 |
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KR1020027014744A KR100845295B1 (ko) | 2000-05-02 | 2001-04-27 | 폴리머 막 |
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US (3) | US7358288B2 (ko) |
EP (1) | EP1282657B1 (ko) |
JP (4) | JP2003532756A (ko) |
KR (1) | KR100845295B1 (ko) |
CN (1) | CN100569837C (ko) |
AT (1) | ATE286090T1 (ko) |
AU (1) | AU2001260070A1 (ko) |
BR (1) | BR0110561A (ko) |
CA (1) | CA2408381C (ko) |
DE (3) | DE10021106A1 (ko) |
ES (1) | ES2238439T3 (ko) |
WO (1) | WO2001084657A2 (ko) |
Cited By (1)
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US9533264B2 (en) | 2012-12-06 | 2017-01-03 | Samsung Electronics Co., Ltd. | Composite membrane, method of manufacturing the same, separation membrane including the composite membrane, and water treatment device using the separation membrane |
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CN103087318B (zh) * | 2013-01-23 | 2015-09-09 | 中国科学技术大学 | 一种侧链磺酸化的聚砜及其制备方法 |
CN103633270B (zh) * | 2013-11-05 | 2016-01-20 | 舟山市金秋机械有限公司 | 无机/有机穿插型复合质子交换膜及其制备方法 |
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-
2000
- 2000-05-02 DE DE10021106A patent/DE10021106A1/de not_active Withdrawn
-
2001
- 2001-04-27 US US10/275,114 patent/US7358288B2/en not_active Expired - Lifetime
- 2001-04-27 WO PCT/DE2001/001624 patent/WO2001084657A2/de active IP Right Grant
- 2001-04-27 AT AT01933631T patent/ATE286090T1/de active
- 2001-04-27 AU AU2001260070A patent/AU2001260070A1/en not_active Abandoned
- 2001-04-27 BR BR0110561-2A patent/BR0110561A/pt not_active IP Right Cessation
- 2001-04-27 CN CNB018089704A patent/CN100569837C/zh not_active Expired - Fee Related
- 2001-04-27 KR KR1020027014744A patent/KR100845295B1/ko not_active IP Right Cessation
- 2001-04-27 DE DE50104970T patent/DE50104970D1/de not_active Expired - Lifetime
- 2001-04-27 ES ES01933631T patent/ES2238439T3/es not_active Expired - Lifetime
- 2001-04-27 DE DE10191702T patent/DE10191702D2/de not_active Expired - Fee Related
- 2001-04-27 EP EP01933631A patent/EP1282657B1/de not_active Expired - Lifetime
- 2001-04-27 JP JP2001581367A patent/JP2003532756A/ja active Pending
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- 2014-12-03 JP JP2014245434A patent/JP2015091977A/ja active Pending
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US9533264B2 (en) | 2012-12-06 | 2017-01-03 | Samsung Electronics Co., Ltd. | Composite membrane, method of manufacturing the same, separation membrane including the composite membrane, and water treatment device using the separation membrane |
Also Published As
Publication number | Publication date |
---|---|
WO2001084657A3 (de) | 2002-06-06 |
KR100845295B1 (ko) | 2008-07-09 |
DE10021106A1 (de) | 2001-11-08 |
US8168705B2 (en) | 2012-05-01 |
JP2015091977A (ja) | 2015-05-14 |
ATE286090T1 (de) | 2005-01-15 |
JP5707187B2 (ja) | 2015-04-22 |
EP1282657A2 (de) | 2003-02-12 |
CA2408381A1 (en) | 2002-11-01 |
US20080318134A1 (en) | 2008-12-25 |
AU2001260070A1 (en) | 2001-11-12 |
JP2011168785A (ja) | 2011-09-01 |
US20110027691A1 (en) | 2011-02-03 |
US7358288B2 (en) | 2008-04-15 |
JP2003532756A (ja) | 2003-11-05 |
BR0110561A (pt) | 2003-12-30 |
EP1282657B1 (de) | 2004-12-29 |
DE10191702D2 (de) | 2003-05-22 |
ES2238439T3 (es) | 2005-09-01 |
CA2408381C (en) | 2011-01-25 |
JP2018035357A (ja) | 2018-03-08 |
CN100569837C (zh) | 2009-12-16 |
CN1427864A (zh) | 2003-07-02 |
US20040106044A1 (en) | 2004-06-03 |
DE50104970D1 (de) | 2005-02-03 |
WO2001084657A2 (de) | 2001-11-08 |
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