CN102803341A - 芳香族聚醚砜嵌段共聚物 - Google Patents
芳香族聚醚砜嵌段共聚物 Download PDFInfo
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- CN102803341A CN102803341A CN2010800265661A CN201080026566A CN102803341A CN 102803341 A CN102803341 A CN 102803341A CN 2010800265661 A CN2010800265661 A CN 2010800265661A CN 201080026566 A CN201080026566 A CN 201080026566A CN 102803341 A CN102803341 A CN 102803341A
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- segmented copolymer
- sulfone
- aromatic polyether
- polyether sulfone
- hydrophilic segment
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- 125000003118 aryl group Chemical group 0.000 title claims abstract description 50
- 239000004695 Polyether sulfone Substances 0.000 title claims abstract description 40
- 229920006393 polyether sulfone Polymers 0.000 title claims abstract description 40
- 229920001400 block copolymer Polymers 0.000 title abstract 2
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 21
- 125000000542 sulfonic acid group Chemical group 0.000 claims abstract description 15
- 229920001577 copolymer Polymers 0.000 claims description 63
- 238000006277 sulfonation reaction Methods 0.000 claims description 20
- 239000012634 fragment Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000000446 fuel Substances 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- 229920000867 polyelectrolyte Polymers 0.000 claims description 15
- -1 benzene sulfone Chemical class 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 description 20
- 238000002360 preparation method Methods 0.000 description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 14
- 229920000491 Polyphenylsulfone Polymers 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 11
- 229910052783 alkali metal Inorganic materials 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical group CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000006575 electron-withdrawing group Chemical group 0.000 description 5
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 150000003457 sulfones Chemical class 0.000 description 4
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 3
- 241000894006 Bacteria Species 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002798 polar solvent Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 229920005604 random copolymer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002522 swelling effect Effects 0.000 description 3
- NYKRSGJRIJJRRK-UHFFFAOYSA-N 1-chloro-2-(2-chlorophenyl)sulfonylbenzene Chemical compound ClC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1Cl NYKRSGJRIJJRRK-UHFFFAOYSA-N 0.000 description 2
- DQFSSJGXWZMREB-UHFFFAOYSA-N 1-fluoro-2-(2-fluorophenyl)sulfonylbenzene Chemical compound FC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1F DQFSSJGXWZMREB-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 241000700605 Viruses Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- IMHDGJOMLMDPJN-UHFFFAOYSA-N biphenyl-2,2'-diol Chemical compound OC1=CC=CC=C1C1=CC=CC=C1O IMHDGJOMLMDPJN-UHFFFAOYSA-N 0.000 description 2
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 238000010612 desalination reaction Methods 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001728 nano-filtration Methods 0.000 description 2
- DFQICHCWIIJABH-UHFFFAOYSA-N naphthalene-2,7-diol Chemical compound C1=CC(O)=CC2=CC(O)=CC=C21 DFQICHCWIIJABH-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 238000001542 size-exclusion chromatography Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 2
- LKFIWRPOVFNPKR-UHFFFAOYSA-N (2-fluorophenyl)-(4-fluorophenyl)methanone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=CC=C1F LKFIWRPOVFNPKR-UHFFFAOYSA-N 0.000 description 1
- NSGXIBWMJZWTPY-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropane Chemical compound FC(F)(F)CC(F)(F)F NSGXIBWMJZWTPY-UHFFFAOYSA-N 0.000 description 1
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 description 1
- QBNABJXQGRVIRA-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)sulfonylbenzene Chemical compound C1=CC(Br)=CC=C1S(=O)(=O)C1=CC=C(Br)C=C1 QBNABJXQGRVIRA-UHFFFAOYSA-N 0.000 description 1
- AVGQIRXZUNRSAY-UHFFFAOYSA-N 1-iodo-4-(4-iodophenyl)sulfonylbenzene Chemical compound C1=CC(I)=CC=C1S(=O)(=O)C1=CC=C(I)C=C1 AVGQIRXZUNRSAY-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- IXUNOARWYRWIAB-UHFFFAOYSA-N 2-fluoro-5-(4-fluoro-3,5-dimethylphenyl)sulfonyl-1,3-dimethylbenzene Chemical compound CC1=C(F)C(C)=CC(S(=O)(=O)C=2C=C(C)C(F)=C(C)C=2)=C1 IXUNOARWYRWIAB-UHFFFAOYSA-N 0.000 description 1
- LSQARZALBDFYQZ-UHFFFAOYSA-N 4,4'-difluorobenzophenone Chemical compound C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 LSQARZALBDFYQZ-UHFFFAOYSA-N 0.000 description 1
- DZXRPCNJQDADRH-UHFFFAOYSA-N 4-chloro-1-(4-chloro-2-methylphenyl)sulfonyl-2-methylbenzene Chemical compound CC1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1C DZXRPCNJQDADRH-UHFFFAOYSA-N 0.000 description 1
- WQRGKOPKPSFHHP-UHFFFAOYSA-N 4-fluoro-1-(4-fluoro-2-methylphenyl)sulfonyl-2-methylbenzene Chemical compound CC1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1C WQRGKOPKPSFHHP-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- UBXYXCRCOKCZIT-UHFFFAOYSA-N biphenyl-3-ol Chemical compound OC1=CC=CC(C=2C=CC=CC=2)=C1 UBXYXCRCOKCZIT-UHFFFAOYSA-N 0.000 description 1
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical compound C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 1
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- NJBFOOCLYDNZJN-UHFFFAOYSA-N pipobroman Chemical compound BrCCC(=O)N1CCN(C(=O)CCBr)CC1 NJBFOOCLYDNZJN-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000412 polyarylene Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920005649 polyetherethersulfone Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000012899 standard injection Substances 0.000 description 1
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
- C08G75/20—Polysulfones
- C08G75/23—Polyethersulfones
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
- C08L81/06—Polysulfones; Polyethersulfones
-
- 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
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/0204—Non-porous and characterised by the material
- H01M8/0221—Organic resins; Organic polymers
-
- 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
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
-
- 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
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Fuel Cell (AREA)
- Polyethers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
本发明涉及一种芳香族聚醚砜嵌段共聚物,包含含有磺酸基团的亲水片段和不含磺酸基团的疏水片段,其中亲水片段的重量比例为0.02至0.35。
Description
本发明涉及芳香族聚醚砜嵌段共聚物、其制备方法及其在燃料电池中或作为水处理膜的用途。
基于芳香族聚醚砜嵌段共聚物的聚电解质用于固体聚合物燃料电池的用途是本身已知的。合适的共聚物描述于EP-A-1394879。它们特别是已使用浓硫酸在室温磺化的聚醚砜(PES)-聚苯砜(PPSU)嵌段共聚物。亲水片段与疏水片段之比在0.6至2.0的范围内并且亲水片段的重量比例高于0.375。
US 2004/0138387涉及嵌段共聚物及其作为聚合物电解质用于燃料电池的用途。磺化用浓硫酸在40至60℃的温度下进行。所述聚合物为,特别是,聚醚醚砜。
EP-A-1113517涉及聚合物电解质及其制备方法。在此,例如,制备二(羟基苯基)砜、二羟基二苯基砜和二(氯苯基)砜的嵌段共聚物,然后用浓硫酸进行磺化。
类似聚合材料还用于制备使水脱盐的膜。Angew.Chem.Int.Ed.2008,47,1至7页描述了使水脱盐的耐氯聚合物。它们是由二磺化单体与未磺化单体制备的聚亚芳基醚砜共聚物。
本发明的一个目的是提供改进的芳香族聚醚砜嵌段共聚物,其可作为聚电解质用于制备燃料电池或作为膜用于水处理。所述聚合物应表现出改进的使用性质或合适的性质特征,特别是在质子导电性、甲醇渗透性和溶胀性方面。对于水处理,其还应具有良好的耐化学性和耐污垢性。
该目的根据本发明通过芳香族聚醚砜嵌段共聚物实现,所述芳香族聚醚砜嵌段共聚物包含含有磺酸基团的亲水片段和不含磺酸基团的疏水片段,其中亲水片段的重量比例为0.02至0.35,基于全部嵌段共聚物计(相当于2至35重量%)。
该目的还通过制备所述芳香族聚醚砜嵌段共聚物的方法实现,其中将一种芳香族聚醚砜嵌段共聚物使用浓硫酸在20至70℃范围的温度下磺化。
该目的还通过上述芳香族聚醚砜嵌段共聚物作为聚电解质用于制备燃料电池或用于制备水处理膜的用途实现。
本发明还提供了包含上述芳香族聚醚砜嵌段共聚物作为聚电解质的燃料电池。
本发明还提供了包含上述芳香族聚醚砜嵌段共聚物的水处理膜。
本发明的芳香族聚醚砜嵌段共聚物具有有利的机械和化学使用性质谱,使其既适于作为聚电解质又适于制备膜。
以下更详细地描述优选的嵌段共聚物及其制备。
在本发明的嵌段共聚物中,亲水片段与疏水片段区别在于,亲水片段含有磺酸基团,而疏水片段不含磺酸基团。亲水片段的重量比例在0.02至0.35、优选0.05至0.30范围内。
在本发明的一个实施方案中,所述重量比例为0.15至0.35。所述嵌段共聚物适于,特别是,作为聚电解质用于制备燃料电池。
在本发明的另一个实施方案中,所述重量比例为0.02至0.25。所述重量比例总是基于全部嵌段共聚物计。所述嵌段共聚物适于,特别是,制备水处理膜。
就本发明而言,亲水片段为含有磺酸基团的片段。相应地,疏水片段为不含任何磺酸基团的片段。
所述亲水片段可由任何芳香族亲水片段组成,只要其含有磺酸基团并且适于制备具有疏水片段的嵌段共聚物即可。
所述亲水片段优选包含磺化的聚亚苯砜(PPSU)链节(buildingblock)。其优选地具有通式(2)
其中R1为C(=O)或S(=O)2,Ar为二价芳基并且m为3至1500、优选5至500间的一个整数。基团Ar也可具有EP-A-1394879中对于通式(2)的结构所给出的含义。
R1优选为S(=O)2。
所述芳基Ar优选为多环芳基,优选通式(3)的联苯基
因此特别优选聚苯基砜基团。
在通式(3)的联苯基团中,苯基之间也可经由-C(CH3)2-基团连接。
通式(2)的基团通过之后的磺化而转化成亲水片段。特别优选的是磺化后式(3)的每一个亚苯基基团均带有一个磺酸基团。该磺酸基团优选存在于连接该基团的氧的邻位。
疏水片段优选为聚醚砜片段。所述疏水片段优选具有通式(1)
其中n为3至1500的一个整数。
所述聚醚砜特别优选具有式(4)
根据本发明,首先制备嵌段共聚物,特别是由聚醚砜单元和聚苯基砜单元组成的嵌段共聚物,然后使用含水的浓硫酸(约98%浓度)将所得嵌段共聚物选择性地磺化。在此优选地仅使上述式(3)的基团磺化。
在本发明的芳香族聚醚砜嵌段共聚物的制备中,优选地将所述芳香族聚醚砜嵌段共聚物使用浓硫酸在20至70℃、优选25至50℃范围的温度下磺化。
所述聚醚砜嵌段和聚苯砜嵌段优选地以这样一种方式存在于本发明的嵌段共聚物中——使所述聚合物嵌段表现出大约10至100nm的相分离。相较于无规共聚物,磺化的嵌段共聚物PES/sPPSU在上述10至100nm范围内具有强的分离的优点。
由于在纳米范围内的相分离,嵌段共聚物可同时获得诸如机械稳定性、薄板在水/甲醇中的低溶胀性和高渗水性或高离子导电性等优点。借助无规共聚物不能获得这些有时彼此抵抗的性质的组合。例如,PPSU含量大于20%的无规PES-PPSU共聚物在磺化后如果可以分离,也只能非常困难地分离,因为它们在水中具有强溶胀性或溶解性。PPSU含量最高达35重量%的嵌段共聚物总是可以分离的。
M优选地为5至500范围内的一个数。
特别优选对应于EP-A-1394879中记载的式(7)的亲水片段和对应于其中记载的式(8)的疏水片段。
本发明的嵌段共聚物的磺酸基团的离子交换容量优选地为0.07至1.43mmol/g,特别优选0.178至1.07mmol/g。
本发明的芳香族聚醚砜嵌段共聚物的制备通过首先合成未磺化的嵌段共聚物,然后将其磺化而实现。
芳香族聚醚砜可用作具有疏水片段的预聚物。其例如通过二羟基酚的二碱金属盐与芳香族二卤化物的反应获得,如R.N.Johnson et al.,J.Polym.Sci.,A-1,Vol.5,2375(1976)和JP-B-46-21458中所教导的。
所述芳香族二卤化物包括二(4-氯苯基)砜、二(4-氟苯基)砜、二(4-溴苯基)砜、二(4-碘苯基)砜、二(2-氯苯基)砜、二(2-氟苯基)砜、二(2-甲基-4-氯苯基)砜、二(2-甲基-4-氟苯基)砜、二(3,5-二甲基-4-氯苯基)砜和二(3,5-二甲基-4-氟苯基)砜。它们可单独使用或以其两种或更多种的结合的形式使用。在这些化合物中,优选二(4-氯苯基)砜和二(4-氟苯基)砜。
所述二羟基醇包括二(4-羟苯基)砜和二(4-羟苯基)酮,优选二(4-羟苯基)砜。
二羟基酚的二碱金属盐可通过二羟基酚与碱金属化合物(例如碳酸钾、氢氧化钾、碳酸钠或氢氧化钠)的反应而获得。
二(4-羟苯基)砜的钠盐或钾盐与二(4-氯苯基)砜或二(4-氟苯基)砜的结合物是二羟基酚的二碱金属盐与芳香族二卤化物的优选结合物。
二羟基酚的二碱金属盐与芳香族二卤化物的反应在极性溶剂中进行,所述极性溶剂例如二甲基亚砜、环丁砜、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺和二苯砜。反应温度优选140至320℃。反应时间优选0.5小时至100小时。
过量使用二羟基酚或芳香族二卤化物可形成端基,这可用于监测预聚物的分子量和合成嵌段共聚物。否则,以等摩尔量使用二羟基酚或芳香族二卤化物,并加入单羟基酚(例如苯酚、甲苯酚、4-苯基苯酚或3-苯基苯酚)或芳香族卤化物(例如4-氯苯基苯基砜、1-氯-4-硝基苯、1-氯-2-硝基苯、1-氯-3-硝基苯、4-氟二苯甲酮、1-氟-4-硝基苯、1-氟-2-硝基苯或1-氟-3-硝基苯)。
所述预聚物的聚合度在3至1500、优选5至500范围内。聚合度小于3时,由此合成的嵌段共聚物几乎不表现出所需性质。聚合度大于1500时,难以合成所述嵌段共聚物。
由于连接有吸电子基团的芳香环难以磺化,优选由疏水片段组成的预聚物,所述疏水片段的芳香环上连接有吸电子基团,例如C(=O)或S(=O)2。由疏水片段组成的优选预聚物具有化学式(1)所示的结构:
其中n为3至1500间的一个整数。
方法(1)中使用的由未磺化的亲水片段组成的预聚物优选地由芳香族二卤化物和芳香环上不含吸电子基团的二羟基酚合成。所述芳香环上不含吸电子基团的二羟基酚包括氢醌、间苯二酚、1,5-二羟基萘、1,6-二羟基萘、1,7-二羟基萘、2,7-二羟基萘、4,4’-二苯酚、2,2’-二苯酚、二(4-羟苯基)醚、二(2-羟苯基)醚、2,2-二(4-羟苯基)-丙烷、2,2-二(3-甲基-4-羟苯基)丙烷、2,2-二(3,5-二甲基-4-羟苯基)丙烷、二(4-羟苯基)甲烷、2,2-二(3,5-二甲基-4-羟苯基)六氟丙烷和9,9-二(4-羟苯基)芴。其中,优选氢醌、间苯二酚、1,5-二羟基萘、1,6-二羟基萘、1,7-二羟基萘、2,7-二羟基萘、4,4’-二苯酚、2,2’-二苯酚、二(4-羟苯基)醚、二(2-羟苯基)醚和9,9-二(4-羟苯基)芴。
芳香族二卤化物包括具有利于合成疏水片段的预聚物的磺基的那些和具有酮基的那些,例如4,4’-二氟二苯甲酮和2,4’-二氟二苯甲酮。最有利的未磺化疏水片段的预聚物具有化学式(2)的结构:
其中R1为C(=O)或S(=O)2;Ar为二价芳基;m为3至1500间的一个整数。
市售的聚合物的分子量和末端基团的改变可通过与上述的二羟基酚或单羟基酚的碱金属盐在与合成芳香族聚醚砜相同的条件下进行醚交换而实现,这描述于R.N.Johnson et al.,J.Polym.Sci.A-1,Vol.5,2375(1967)或JP-46-21458。
未磺化的嵌段共聚物通过使上述疏水片段的预聚物与未磺化的亲水片段的预聚物反应而合成。优选具有卤素末端基团或酚的碱金属盐末端基团的疏水片段的预聚物。优选的是,未磺化的亲水片段的预聚物具有相应的卤素末端基团或相应的酚的碱金属盐末端基团。该反应在上述溶剂中在140至320℃的反应温度下进行0.5小时至100小时。该反应描述于,例如,Z.Wu et al.,Angew.Makromol.Chem.,Vol 173,163(1989)和Z.Wang et al.,Polym.Int.Vol.50,249(2001)。
未磺化嵌段共聚物也可通过使用偶联剂使各自具有酚的碱金属盐末端基团的两个片段预聚物之间以相同的方式反应而合成。上述芳香族二卤化物可用作偶联剂。芳香族二氟化物,例如二(2-氟苯基)砜和二(4-氟苯基)砜,因其高反应性而优选作为偶联剂。产物可由于直接偶联而磺化。
根据本发明,磺化在20至70℃的温度下借助硫酸进行。硫酸的浓度优选为90至98重量%,特别是98重量%。在该温度范围内,只有亲水片段被成功磺化,因为疏水片段具有连于芳环的吸电子基团而不能被磺化。
因此,在完全磺化的情况下,磺化程度通过在缩聚中引入的聚苯砜(PPSU)片段确定。在磺化过程中,所有PPSU嵌段均完全磺化。磺化程度可通过PES/PPSU嵌段共聚物的摩尔质量和片段长度而非常容易地设定。
相较于无规共聚物,本发明的磺化嵌段共聚物具有强的相分离的优点。聚合物嵌段优选地表现出大约10至100nm的相分离。
本发明聚合物的重均分子量(Mw),基于未磺化的聚合物计,在1至200kg/mol、特别优选5至100kg/mol、特别是5至70kg/mol的范围内,由凝胶渗透色谱法/尺寸排阻色谱法确定。所述方法是本领域技术人员熟知的并且对应于研究现状。
测量条件选择如下:将聚合物以2g/L的浓度溶解在DMAc(二甲基乙酰胺)中,加入0.5%的盐。通过孔径为0.2μm的标准注射过滤器对溶液进行预过滤。80℃柱温下的注射量为200μl。尺寸排阻色谱法用若干柱的组合进行(针对选定的柱组合和流速而计算的理论板数为17200)。信号借助差示折光计检测(确定折射率)。使用分子量M=800至M=1820000g/mol来自PSS的窄分布PMMA标准物进行校准。测量的所有值都在标准范围内。
本发明还提供上述芳香族聚醚砜嵌段共聚物作为聚电解质用于制备燃料电池或用于制备水处理膜的用途。聚电解质膜在燃料电池中的用途是公知的。在此可参考,例如EP-A-1394879、EP-A-1113517、US2004/0138387、EP-A-1669391和EP-A-1855339。聚电解质膜可例如通过薄膜形成方法使用本发明的嵌段共聚物获得。
由以此方式制备的芳香族聚醚砜的嵌段共聚物起始来形成薄膜以获得本发明的含固体聚合物燃料的电池的聚电解质膜的方法不受任何具体方式的限制。例如,可将芳香族聚醚砜的嵌段共聚物溶解于极性溶剂中,例如二甲基亚砜、环丁砜、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二苯砜,将溶液倒在载体上然后通过例如蒸发除去(极性)溶剂。薄膜厚度为5至200μm,优选10至150μm。薄于5μm的薄膜通常难以处理。厚于200μm的薄膜是不利的,因为包含这种膜的燃料电池表现出减少的发电(power generation)效率。
如果需要,本发明的聚电解质膜中的一部分磺酸基团可以以金属盐的形式存在,只要不损害本发明的性质即可。此外,所述膜可借助纤维、多孔膜等来增强。如果必要,聚电解质膜可包含可以彼此混合的无机酸(例如磷酸、次磷酸和硫酸)或其盐、含有1至14个碳原子的全氟烷基磺酸或其盐、含有1至14个碳原子的全氟烷基羧酸或其盐、无机物质(例如铂、硅胶、二氧化硅和沸石)和其他聚合物。
燃料电池的制备不受任何限制。
膜-电极组件(MEA)可通过与气体扩散电极(GDE)一起压制或通过直接涂以催化剂溶液,例如通过丝网印刷(screen printing)而制备。这得到催化剂涂布膜(catalyst coated membrane)(CCM)。
本发明的芳香族聚醚砜嵌段共聚物也可用于制备水处理膜。这类膜的制备例如述于Angew.Chem.Int.Ed.2008,47,1至7页。所述膜特别是通过将聚合物溶液浇铸在诸如玻璃板的平坦基材上,然后移除溶剂而制备。溶剂的移除可例如以加热或通过施加减压来进行。
水处理膜通常是半渗透膜,其可从水中分离出溶解和悬浮的颗粒,分离过程本身能够通过压力或电驱动。本发明聚合物的常见而非限制性的膜使用实例为压力驱动膜技术,例如微滤(MF;分离限度为约0.08至2μm;极小的悬浮颗粒、胶体、细菌)、超滤(UF;分离限度为约0.005至0.2μm;>1000MW的有机颗粒,病毒、细菌、胶体)、纳米过滤(nanofiltration)(NF,分离限度为0.001至0.01μm,>300MW的有机颗粒,THM前体、病毒、细菌、胶体、溶解物质)或反渗透(RO,分离限度为0.0001至0.001μm,离子、>100MW的有机物)。所有膜的制备均可由本发明的聚合物进行。
所有膜的制备途径均是文献中已知的,例如由M.C.Porter等人述于Handbook of Industrial Membrane Technology(William AndrewPublishing/Noyes,1990)中。本发明聚合物在系统中最常用的非限制性构造实例为由中空纤维组成的过滤模块(filtration module)或卷式膜模块(wound membrane module)。这些同样是本领域技术人员已知的,并且述于文献中(见上文)。
由本发明聚合物制备水处理领域内用于各种应用的膜的可行但非限制性方式记载在Handbook of Industrial Technology(由Mark C.Proter汇编,Pleasanton,California Reprint Edition Noyes Publications,Westwood,New Jersey,USA)的图1-1中。
本发明还提供相应的包含本发明的芳香族聚醚砜嵌段共聚物作为聚电解质的燃料电池和包含本发明的芳香族聚醚砜嵌段共聚物作为膜材料的水处理膜。
Claims (12)
1.一种芳香族聚醚砜嵌段共聚物,包含含有磺酸基团的亲水片段和不含磺酸基团的疏水片段,其中所述亲水片段的重量比例为0.02至0.35。
2.权利要求1的嵌段共聚物,其中所述亲水片段的重量比例为0.15至0.35。
3.权利要求1的嵌段共聚物,其中所述亲水片段的重量比例为0.02至0.25。
4.权利要求1至3中任一项的嵌段共聚物,其中所述疏水片段包含聚醚砜链节。
6.权利要求1至5中任一项的嵌段共聚物,其中所述亲水片段包含磺化的聚亚苯砜链节。
8.权利要求1至7中任一项的嵌段共聚物,其中所述聚合物嵌段表现出大约10至100nm的相分离。
9.一种制备权利要求1至8中任一项的芳香族聚醚砜嵌段共聚物的方法,其中将一种芳香族聚醚砜嵌段共聚物使用浓硫酸在20至70℃范围的温度下磺化。
10.权利要求1至8中任一项的芳香族聚醚砜嵌段共聚物作为聚电解质用于制备燃料电池或用于制备水处理膜的用途。
11.一种燃料电池,包含一种权利要求1至8中任一项的芳香族聚醚砜嵌段共聚物作为聚电解质。
12.一种水处理膜,包含一种权利要求1至8中任一项的芳香族聚醚砜嵌段共聚物。
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EP (1) | EP2443172B1 (zh) |
JP (1) | JP2012530166A (zh) |
KR (1) | KR20120044973A (zh) |
CN (1) | CN102803341A (zh) |
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CN103936991A (zh) * | 2013-01-22 | 2014-07-23 | 曹曙光 | 至少含一个亲水嵌段组分的共聚物聚电解质及合成方法 |
CN103936990A (zh) * | 2013-01-22 | 2014-07-23 | 曹曙光 | 至少含一个憎水嵌段组分的共聚物聚电解质及合成方法 |
CN105705221A (zh) * | 2013-09-16 | 2016-06-22 | 株式会社Lg化学 | 包含可离子交换聚合物层的水处理分离膜及其形成方法 |
CN109692582A (zh) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | 反渗透膜及其制备方法和应用 |
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WO2010112508A1 (de) | 2009-04-03 | 2010-10-07 | Basf Se | Verfahren zur herstellung von chlorarmen polybiphenylsulfon-polymeren |
WO2010142548A1 (de) | 2009-06-08 | 2010-12-16 | Basf Se | Segmentierte polyarylenether-blockcopolymere |
KR101982949B1 (ko) | 2009-08-20 | 2019-05-27 | 바스프 에스이 | 저-할로겐 폴리비페닐술폰 중합체의 제조 방법 |
WO2011069892A1 (de) | 2009-12-08 | 2011-06-16 | Basf Se | Verfahren zur herstellung von polyamiden |
EP2336220A1 (de) | 2009-12-17 | 2011-06-22 | Basf Se | Verbesserte Blends aus Polyarylenethern und Polyarylensulfiden |
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EP2532700A1 (en) * | 2011-06-06 | 2012-12-12 | Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. | Novel block copolymers comprising sulfonated poly(sulfones) with high ion-exchange capacity, high ion-conductivity and high stability |
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- 2010-06-15 WO PCT/EP2010/058390 patent/WO2010146052A1/de active Application Filing
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- 2010-06-15 JP JP2012515462A patent/JP2012530166A/ja active Pending
- 2010-06-15 CN CN2010800265661A patent/CN102803341A/zh active Pending
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CN103936991A (zh) * | 2013-01-22 | 2014-07-23 | 曹曙光 | 至少含一个亲水嵌段组分的共聚物聚电解质及合成方法 |
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CN105705221A (zh) * | 2013-09-16 | 2016-06-22 | 株式会社Lg化学 | 包含可离子交换聚合物层的水处理分离膜及其形成方法 |
CN109692582A (zh) * | 2017-10-20 | 2019-04-30 | 中国石油化工股份有限公司 | 反渗透膜及其制备方法和应用 |
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EP2443172A1 (de) | 2012-04-25 |
WO2010146052A1 (de) | 2010-12-23 |
US20120083541A1 (en) | 2012-04-05 |
KR20120044973A (ko) | 2012-05-08 |
BRPI1015994A2 (pt) | 2016-04-19 |
MY160125A (en) | 2017-02-28 |
EP2443172B1 (de) | 2016-09-21 |
JP2012530166A (ja) | 2012-11-29 |
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