CN1427739A - 有机-无机膜 - Google Patents
有机-无机膜 Download PDFInfo
- Publication number
- CN1427739A CN1427739A CN01808969A CN01808969A CN1427739A CN 1427739 A CN1427739 A CN 1427739A CN 01808969 A CN01808969 A CN 01808969A CN 01808969 A CN01808969 A CN 01808969A CN 1427739 A CN1427739 A CN 1427739A
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- Prior art keywords
- film
- metal
- polymer
- membrane
- organic
- 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.)
- Granted
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- 239000012528 membrane Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 230000007062 hydrolysis Effects 0.000 claims abstract description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 9
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 5
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 10
- 150000001266 acyl halides Chemical class 0.000 claims description 10
- 239000011159 matrix material Substances 0.000 claims description 10
- 238000012805 post-processing Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000004706 metal oxides Chemical class 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 150000004703 alkoxides Chemical class 0.000 claims description 8
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000004692 metal hydroxides Chemical class 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000005595 acetylacetonate group Chemical group 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 229960001760 dimethyl sulfoxide Drugs 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000002360 preparation method Methods 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 239000000010 aprotic solvent Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 125000005594 diketone group Chemical group 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- 150000004027 organic amino compounds Chemical class 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- -1 polyphenylsulphine Polymers 0.000 claims 6
- 150000001412 amines Chemical class 0.000 claims 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 239000004695 Polyether sulfone Substances 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 239000004734 Polyphenylene sulfide Substances 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 1
- 150000003863 ammonium salts Chemical class 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
- 239000004305 biphenyl Substances 0.000 claims 1
- 125000006267 biphenyl group Chemical group 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 238000004132 cross linking Methods 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
- 239000004744 fabric Substances 0.000 claims 1
- 239000011521 glass Substances 0.000 claims 1
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 238000001764 infiltration Methods 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 229910001463 metal phosphate Inorganic materials 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- 238000005373 pervaporation Methods 0.000 claims 1
- 229920001643 poly(ether ketone) Polymers 0.000 claims 1
- 229920006393 polyether sulfone Polymers 0.000 claims 1
- 229920005649 polyetherethersulfone Polymers 0.000 claims 1
- 229920006254 polymer film Polymers 0.000 claims 1
- 229920006380 polyphenylene oxide Polymers 0.000 claims 1
- 229920000069 polyphenylene sulfide Polymers 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims 1
- 210000002268 wool Anatomy 0.000 claims 1
- 229920002959 polymer blend Polymers 0.000 abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 3
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 abstract description 2
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract 2
- 101100084403 Homo sapiens PRODH gene Proteins 0.000 abstract 1
- 229910018828 PO3H2 Inorganic materials 0.000 abstract 1
- 101150059359 POX2 gene Proteins 0.000 abstract 1
- 102100028772 Proline dehydrogenase 1, mitochondrial Human genes 0.000 abstract 1
- 229910006080 SO2X Inorganic materials 0.000 abstract 1
- 229910006069 SO3H Inorganic materials 0.000 abstract 1
- 101100029251 Zea mays PER2 gene Proteins 0.000 abstract 1
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 abstract 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 abstract 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 16
- 239000010936 titanium Substances 0.000 description 9
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 8
- 239000002131 composite material Substances 0.000 description 8
- 229920000554 ionomer Polymers 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 229920001601 polyetherimide Polymers 0.000 description 3
- 229910000077 silane Inorganic materials 0.000 description 3
- 230000008961 swelling Effects 0.000 description 3
- 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 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 230000003252 repetitive effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 229920004738 ULTEM® Polymers 0.000 description 1
- 229920004695 VICTREX™ PEEK Polymers 0.000 description 1
- 125000000777 acyl halide group Chemical group 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- OHMBHFSEKCCCBW-UHFFFAOYSA-N hexane-2,5-diol Chemical compound CC(O)CCC(C)O OHMBHFSEKCCCBW-UHFFFAOYSA-N 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000000887 hydrating effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 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
- 229920000831 ionic polymer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000002245 particle Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003755 zirconium compounds Chemical class 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
-
- 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
- B01D67/00931—Chemical modification by introduction of specific groups after membrane formation, e.g. by grafting
-
- 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
- B01D67/0039—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
- B01D69/12—Composite membranes; Ultra-thin 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
-
- 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
- B01D71/82—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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
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Abstract
本发明涉及有机/无机杂化聚合物共混物和杂化聚合物共混物膜,它们包括:一种含有SO2X,POX2或-COX基团(X=F,Cl,Br,I)的聚合酰基卤,一种元素或金属氧化物或氢氧化物,其是通过在膜形成过程中元素和/或有机金属化合物的水解和/或溶胶/凝胶反应,和/或随后在酸性、碱性或中性的水性电解液中处理该膜得到的。本发明还涉及含有带SO3H,PO3H2和/或COOH基团的聚合物的杂化共混物和杂化共混物膜,其是通过在聚合物共混物或聚合物共混物膜中含有的聚合酰基卤的中性、碱性或酸性水解得到的。本发明还涉及生产所述杂化共混物和杂化共混物膜的方法。
Description
1.发明主题
本发明涉及有机/无机杂化聚合物共混物和杂化聚合物共混物膜,它们包括:
·含有-SO2X,-POX2或-COX基团的聚合酰基卤(X=F,Cl,Br,I)
·元素氧化物或元素氢氧化物或金属氧化物或金属氢氧化物,其是通过在膜形成过程中元素有机化合物和/或金属有机化合物的水解和/或溶胶/凝胶反应,和/或随后在酸性、碱性或中性的水性电解液中处理该膜得到的。
本发明还涉及含有带SO3H,PO3H2和/或COOH基团的聚合物的杂化共混物和杂化共混物膜,其是通过在聚合物共混物或聚合物共混物膜中含有的聚合酰基卤的中性、碱性或酸性水解得到的。
本发明还涉及生产所述杂化共混物和杂化共混物膜的方法。
2.技术状况及其缺点
在下列文献中公开了关于酰基氯/无机杂化复合材料的技术状况:
将Nafion磺酰基氟化物前体膜在全氟氢菲中预溶胀并浸渍在3-氨基丙基三乙氧基硅烷中。然后用EtOH洗掉过量的硅烷。形成杂化物,其中通过硅烷水解和通过硅烷与SO2F基团反应,在膜基质中形成与聚合物部分交联的SiO2网状物(Chemical modification of a nafion sulfonyl fluoride precursorvia in situ sol-gel reactions,A.J.Greso,R.B.Moore,K.M.Cable,W.L.Jarrett,K.A.Mauritz Polymer 38,1345-1356(1 997))。
所述体系的缺点为:溶胶/凝胶反应在预成型的膜中进行,因此不能任意设定通过水解聚合物复合材料形成的无机聚合物相的含量。
在下列文献中还分别描述了非离子聚合物和各金属元素氧化物的杂化体系:
(e)聚甲基丙烯酸正丁酯和氧化钛的复合材料,它是在蒸发掉溶剂后由烷氧基钛在聚合物基质中进行水蒸气水解制得的,所述烷氧基钛被加入到聚甲基丙烯酸正丁酯聚合物溶液的醇溶液中(Novel Poly(n-ButylMethacryate)/Titanium Oxide Alloys Produced by the Sol-Gel process forTitanium Alkoxides,K.A.Mauritz,C.K.Jones,J.Appl.Polym.Sci.40,1401-1420(1990))。
(f)聚醚酰亚胺和纳米分散的氧化硅的复合材料,其是通过向聚醚酰亚胺Ultem的NMP溶液中加入0.15M的HCl溶液水解TEOS制得的。水解后,由该聚合物溶液制得致密的或相反转的膜。通过另外加入3-氨基丙基三甲氧基硅烷(AS)获得无机相与有机相的相容性(Membranes of poly(etherimide)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.)。
3.发明目的
本发明的一个目的是提供含有另外的无机元素/金属氧化物/氢氧化物相的聚合酰基卤的复合材料和复合材料膜,其改善了下列的膜性能:
·机械稳定性
·热稳定性
·改善的持水能力,即使在>100℃的温度下,这一点是重要的,特别是对于在>100℃的温度范围内在膜燃料电池中的应用。
在根据本发明的方法中,元素/金属氧化物/氢氧化物的有机前体被引入到聚合物溶液中(烷氧化物/酯,乙酰丙酮化物等)。
在离子交联聚合物中无机相的形成发生在通过在酸性、碱性和/或中性水环境下水解形成膜之后,而任选发生在聚合酰基卤可被水解为酸基团的同时或另一步中。4.本发明解决的目标(发明内容)
已令人惊奇地发现,如果将在1-丙醇中的70重量%的丙醇锆(IV)Zr(OCH2CH2CH3)4引入到PSU磺酰氯的四氢呋喃溶液中,丙醇锆(IV)在聚合物溶液中不会水解或形成保守的可溶的络合物,但当溶剂蒸发时形成膜基质。如果将丙醇锆(IV)的丙醇溶液和PSU磺酰氯(或PSU磺酸或PSU磺酸盐)在偶极非质子溶剂例如N-甲基吡咯烷二酮中的溶液混合,丙醇锆(IV)将立刻水解或沉淀。已令人惊奇地发现,通过连续地在碱性水溶液和/或水和/或酸中后处理膜,可将有机锆化合物水解成在膜基质中纳米分散的二氧化锆或氧化锆氢氧化物。采用EDX在膜基质中可检测到该无机锆化合物。其它的有机金属化合物,如Ti(acac)2(OiPr)2也可与PSU磺酰氯在醚溶剂中的溶液混合,而不会在聚合物溶液中水解并通过蒸发溶剂形成膜基质。
可制备根据本发明的下列复合材料。复合材料含有:
·至少一种带-SO2X,-POX2和/或-COX基团的聚合酰基卤,其中X是指F,Cl,Br或I,优选含有芳基主链聚合物骨架,和
·至少一种盐,元素氧化物或元素氢氧化物或金属氧化物或金属氢氧化物,其是通过在膜形成过程中水解下列种类的元素有机化合物和/或金属有机化合物,和/或通过在酸性、碱性或中性的水性电解液中后处理膜得到的:
·Ti,Zr,Sn,Si,B,Al的金属/元素烷氧化物/酯
·金属乙酰丙酮化物,例如Ti(acac)4,Zr(acac)4
·金属/元素烷氧化物和金属乙酰丙酮化物的混合化合物,例如
Ti(acac)2(OiPr)2等
·Ti,Zr,Sn,Si,B,Al的有机氨基化合物采用相同的后处理步骤或采用另一种水性的酸性、碱性或中性后处理步骤,酰基卤基团可由此任选水解成相应的酸基团,得到含有另外的纳米分散分布的无机相的离子交联聚合物(共混物)膜。
根据本发明可采用下列溶剂制备膜:偶极非质子溶剂,例如N-甲基吡咯烷二酮(NMP),N,N-二甲基乙酰胺(DMAc),N,N-二甲基甲酰胺(DMF),二甲亚砜(DMSO)或环丁砜,或醚溶剂,例如四氢呋喃,二噁烷,甘醇二甲醚,二甘醇二甲醚,三甘醇二甲醚。
由于无机相纳米分散分布在膜基质中,根据本发明其导致酰基卤聚合物(共混物)或传导质子的离子交联聚合物(共混物)的性能与离子交联聚合物(共混物)膜之间的曲线关系被明显改变。质子传导性增加,而溶胀性通常没有相应地增加。
根据纳米分散分布的组分的性质和含量,膜对非离子渗透分子(例如气体)的选择渗透性也会改变。
如果在磷酸中进行水解,或者如果用磷酸进一步后处理膜是在水解后进行的,则产生相应的金属或元素磷酸盐或磷酸氢盐或磷酸二氢盐,其中的一部分对质子传导性有贡献。
5.实施例5.1 离子交联聚合物共混物膜TH785的制备
将每个重复单元含有约1个磺酰氯基团的0.5g PSU磺酰氯溶解在3gTHF中。然后,加入0.5307g 70重量%的丙醇锆(IV)的1-丙醇溶液。对该溶液脱气,然后将其注塑成陪替氏培养皿。在室温下过夜蒸发溶剂。之后,对形成的膜进行如下的后处理:(1)在80℃的10%NaOH中处理24小时,(2)在80℃的10%硫酸中处理24小时,(3)在85℃的水中处理16小时。结果表征:IEC[毫克当量SO3H/g]: 0,77溶胀[%]: 30.9Rsp H+(0,5N HCl)[Ωcm]: 28,95.2 离子交联聚合物共混物膜TH782的制备
将每个重复单元含有约1个磺酰氯基团的0.5g PSU磺酰氯溶解在2.5gTHF中。然后,加入0.8817g 75重量%的双(乙酰丙酮根)二异丙醇钛(IV)的2-丙醇溶液。对该溶液脱气,然后将其注塑成陪替氏培养皿。在室温下过夜蒸发溶剂。之后,对形成的膜进行如下的后处理:(4)在80℃的10%NaOH中处理24小时,(5)在80℃的10%硫酸中处理24小时,(6)在85℃的水中处理16小时。结果表征:IEC[毫克当量SO3H/g]: 0,81溶胀[%]: 39,4Rsp H+(0.5N HCl)[Ωcm]: 12
6.发明的新颖性
本发明的新型无机/有机杂化离子交联聚合物(共混物)膜及其制备方法没有在文献中公开过,既没有被申请人公开过,也没有被其它出版物公开过。7.发明的优点
本发明的新型无机/有机杂化膜显示出优异的性能:·良好的质子传导性·良好的热稳定性·良好的机械稳定性·有限的溶胀性。
本发明的一些膜显示出改善的持水能力,特别是在T>80℃的条件下,这是由在膜基质中的无机氧化物/氢氧化物导致的。可以推测无机组分在膜中的纳米分散是其背后的原因。如同在某些出版物中已提议的那样(Comparison of Ethanol and Methanol Oxidation in a Liquid-Feed SolidPolymer Electrolyte Fuel Cell at High Temperature,A.S.Arico,P.Creti,P.L.Antonucci,V.Antonucci,Electrochem.Sol.St.Lett,182)66-68(1998)),通过将氧化物粉末混入离子交联聚合物膜中,不能实现使无机组分在膜基质中象本发明方法那样的精细分布,其中元素有机化合物/金属有机化合物在膜基质中仅水解为氧化物或磷酸(氢)盐。取决于特定的组成,本发明的膜还显示出下列优点:·降低的甲醇渗透性·对质子传导性的贡献,特别是在T>80℃的条件下·改变带电和非带电颗粒的选择渗透性·膜是光化学活性的,特别是那些含有纳米分散的二氧化钛的膜·特定的组成(含有二氧化钛)显示光致发光性8.关键词芳基主链聚合物溶胶/凝胶方法水解Ti,Zr,Sn,Si,B,Al的金属和元素烷氧化物金属和元素乙酰丙酮化物Ti(acac)4,Zr(acac)4金属/元素烷氧化物和金属乙酰丙酮化物的混合化合物Ti(acac)2(OiPr)2Ti,Zr,Sn,Si,B,Al的有机氨基化合物元素氧化物金属氧化物元素氢氧化物金属氢氧化物含水的氧化物含水的磷酸盐持水能力质子传导性聚砜Udel聚醚醚酮Victrex聚合酰基卤阳离子交换聚合物阳离子交换聚合物膜聚合物质子导体质子本身传导性膜燃料电池H2燃料电池直接甲醇燃料电池膜膜工艺应用温度>80℃热稳定性
Claims (15)
1.含有至少一种聚合酰基卤的膜,其特征在于在膜形成过程之前、之中或之后,将盐,金属氧化物或金属氢氧化物或它们的有机前体引入到膜中。
2.根据权利要求1的膜,其特征在于聚合酰基卤是芳基主链聚合物并带有SO2X,POX2或COX或BX2基团(X=F,Cl,Br,I),并且其选自聚醚砜,聚砜,聚苯基砜,聚醚醚砜,聚醚酮,聚醚醚酮,聚苯醚,聚二苯基苯醚,聚苯硫,或为含有这些组分中至少一种的共聚物。
3.根据权利要求1-2中的一项或多项的膜,其特征在于它们含有盐,元素或金属氧化物或金属氢氧化物,其是在膜形成之前、之中或之后通过水解和/或溶胶/凝胶反应得到的,并选自下列前体:
Ti,Zr,Sn,Si,B,Al的金属/元素烷氧化物/酯
金属乙酰丙酮化物,例如Ti(acac)4,Zr(acac)4
金属/元素烷氧化物和金属乙酰丙酮化物的混合化合物,例如Ti(acac)2(OiPr)2等
Ti,Zr,Sn,Si,B,Al的有机氨基化合物。
4.根据权利要求3的膜,其特征在于,通过在膜形成后进行的水解反应将膜聚合物的SO2X,POX2或COX或BX2基团(X=F,Cl,Br,I)变为SO3Y,PO3Y2或COOY或B(OY)2基团(Y=H,一价或二价金属阳离子,铵离子,咪唑鎓离子,吡唑鎓离子,吡啶鎓离子)。
5.根据权利要求1-4中的一项或多项的膜,其特征在于它们是被另外共价交联的。
6.根据权利要求1-5中的一项或多项的膜,其特征在于用磷酸对膜进行后处理,以在膜基质中由金属氧化物和/或金属氢氧化物和/或金属氧化物氢氧化物生成对质子传导性有贡献的金属磷酸盐或元素磷酸盐或金属磷酸氢盐或元素磷酸氢盐或金属磷酸二氢盐或元素磷酸二氢盐。
7.根据权利要求1-6中的一项或多项的膜的制备方法,其特征在于下列组分是在偶极非质子溶剂,例如N-甲基吡咯烷二酮(NMP),N,N-二甲基乙酰胺(DMAc),N,N-二甲基甲酰胺(DMF),二甲亚砜(DMSO)或环丁砜,或在醚溶剂,例如四氢呋喃,二噁烷,甘醇二甲醚,二甘醇二甲醚,三甘醇二甲醚等中混合的:带SO2X,POX2,COX或BX2基团(X=F,Cl,Br,I)的聚合酰基卤,和至少根据权利要求3化合物的金属有机或元素有机化合物。
8.根据权利要求7的方法,其特征在于,在载体(玻璃板或金属板,薄纸,织物或非织物,羊毛,多孔(聚合物)膜)上将权利要求6的聚合物溶液注塑成薄膜,在常压或在真空下于80-150℃的温度下蒸发溶剂,并且对形成的薄膜进行如下的后处理,而后处理步骤的顺序可以改变,并可任选省略掉步骤(1)和/或(2)和/或(3):
(1)在T=50-100℃的水中,
(2)在T=50-100℃的1-100%的无机酸中(氢卤酸,硫酸,磷酸),
(3)在1-50%的碱性水溶液中(例如铵溶液,胺溶液,氢氧化钠溶液,
氢氧化钾溶液,碳酸钠溶液,氢氧化钙溶液,氢氧化钡溶液)
或在无水液态胺或不同胺的混合物中,
(4)在T=50-100℃的水中。
9.根据权利要求1的膜通过电化学方法产生能量的应用。
10.根据权利要求1的膜通过光化学方法产生能量或物质的应用。
11.根据权利要求1的膜在0-180℃的温度下作为膜燃料电池(H2或直接甲醇燃料电池)构件的应用。
12.根据权利要求1的膜在电化学电池中的应用。
13.根据权利要求1的膜在二次电池中的应用。
14.根据权利要求1的膜在电解电池中的应用。
15.根据权利要求1的膜在膜分离方法,例如气体分离,全蒸发,全提取,反渗透,电渗析和扩散透析中的应用。
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DE10021104A DE10021104A1 (de) | 2000-05-02 | 2000-05-02 | Organisch-anorganische Membranen |
DE10021104.6 | 2000-05-02 | ||
PCT/EP2001/004907 WO2001083092A1 (de) | 2000-05-02 | 2001-05-02 | Organisch-anorganische membranen |
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CN1427739B CN1427739B (zh) | 2010-05-26 |
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US (2) | US20040101760A1 (zh) |
EP (2) | EP2047899A1 (zh) |
JP (1) | JP5037773B2 (zh) |
KR (1) | KR100915021B1 (zh) |
CN (1) | CN1427739B (zh) |
AT (1) | ATE372165T1 (zh) |
AU (1) | AU2001256331A1 (zh) |
BR (1) | BRPI0110562B1 (zh) |
CA (1) | CA2407509C (zh) |
DE (2) | DE10021104A1 (zh) |
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Cited By (2)
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CN102378645A (zh) * | 2009-03-31 | 2012-03-14 | 东丽株式会社 | 复合半透膜及其制造方法 |
CN102378645B (zh) * | 2009-03-31 | 2014-06-04 | 东丽株式会社 | 复合半透膜及其制造方法 |
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KR100915021B1 (ko) | 2009-09-02 |
US7387732B2 (en) | 2008-06-17 |
ATE372165T1 (de) | 2007-09-15 |
US20040101760A1 (en) | 2004-05-27 |
US20060096913A1 (en) | 2006-05-11 |
BRPI0110562B1 (pt) | 2015-09-01 |
EP1278590A1 (de) | 2003-01-29 |
WO2001083092A1 (de) | 2001-11-08 |
CA2407509A1 (en) | 2001-11-08 |
CA2407509C (en) | 2012-02-21 |
JP5037773B2 (ja) | 2012-10-03 |
JP2004501229A (ja) | 2004-01-15 |
EP2047899A1 (de) | 2009-04-15 |
DE10021104A1 (de) | 2001-11-08 |
KR20030015233A (ko) | 2003-02-20 |
EP1278590B1 (de) | 2007-09-05 |
CN1427739B (zh) | 2010-05-26 |
DE50112963D1 (de) | 2007-10-18 |
AU2001256331A1 (en) | 2001-11-12 |
BR0110562A (pt) | 2003-12-30 |
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