CN1301191A - 交联的离子导电膜 - Google Patents
交联的离子导电膜 Download PDFInfo
- Publication number
- CN1301191A CN1301191A CN99806422A CN99806422A CN1301191A CN 1301191 A CN1301191 A CN 1301191A CN 99806422 A CN99806422 A CN 99806422A CN 99806422 A CN99806422 A CN 99806422A CN 1301191 A CN1301191 A CN 1301191A
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- Prior art keywords
- polymer
- crosslinking agent
- replacement
- film
- group
- Prior art date
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- 239000012528 membrane Substances 0.000 title abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 78
- 238000000034 method Methods 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000004971 Cross linker Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims description 80
- 229920006037 cross link polymer Polymers 0.000 claims description 30
- 125000000524 functional group Chemical group 0.000 claims description 28
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 19
- 125000005842 heteroatom Chemical group 0.000 claims description 17
- 229910052698 phosphorus Inorganic materials 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052736 halogen Inorganic materials 0.000 claims description 11
- 125000000777 acyl halide group Chemical group 0.000 claims description 10
- 125000003368 amide group Chemical group 0.000 claims description 9
- 125000005462 imide group Chemical group 0.000 claims description 9
- 150000001408 amides Chemical class 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000001266 acyl halides Chemical class 0.000 claims description 7
- 125000005647 linker group Chemical group 0.000 claims description 7
- 150000001768 cations Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 4
- 125000005843 halogen group Chemical group 0.000 claims 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 2
- 229910021529 ammonia Inorganic materials 0.000 claims 2
- 230000002378 acidificating effect Effects 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 13
- 230000008961 swelling Effects 0.000 abstract description 9
- 238000004132 cross linking Methods 0.000 abstract description 7
- 150000003949 imides Chemical group 0.000 abstract description 3
- 229920002492 poly(sulfone) Polymers 0.000 abstract description 3
- 229920001643 poly(ether ketone) Polymers 0.000 abstract description 2
- 229920001467 poly(styrenesulfonates) Polymers 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 59
- 239000000460 chlorine Substances 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- 239000004696 Poly ether ether ketone Substances 0.000 description 9
- 238000007766 curtain coating Methods 0.000 description 9
- 230000007062 hydrolysis Effects 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 229920002530 polyetherether ketone Polymers 0.000 description 9
- 238000006277 sulfonation reaction Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- 238000002360 preparation method Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 7
- 229910052801 chlorine Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 229910017604 nitric acid Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229920000557 Nafion® Polymers 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical group O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000005357 flat glass Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 229940124530 sulfonamide Drugs 0.000 description 3
- 150000003456 sulfonamides Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical class CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UZGKAASZIMOAMU-UHFFFAOYSA-N 124177-85-1 Chemical compound NP(=O)=O UZGKAASZIMOAMU-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- OWIKHYCFFJSOEH-UHFFFAOYSA-N Isocyanic acid Chemical compound N=C=O OWIKHYCFFJSOEH-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- -1 anionic ion Chemical class 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 238000009838 combustion analysis Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000002523 gelfiltration Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920006380 polyphenylene oxide Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000472 sulfonyl group Chemical class *S(*)(=O)=O 0.000 description 2
- AUVLKYVTAAKSDM-UHFFFAOYSA-N 1,1,2-trifluoro-2-(1,2,2-trifluoroethenylsulfanyl)ethene Chemical compound FC(F)=C(F)SC(F)=C(F)F AUVLKYVTAAKSDM-UHFFFAOYSA-N 0.000 description 1
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- PIOSENMMCZHTGF-UHFFFAOYSA-N 2-benzylidenebut-3-enoic acid Chemical compound OC(=O)C(C=C)=CC1=CC=CC=C1 PIOSENMMCZHTGF-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000010358 mechanical oscillation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 150000002892 organic cations Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical class OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 1
- 239000005052 trichlorosilane Substances 0.000 description 1
- 239000011800 void material Substances 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
- 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
- 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
- B01D71/52—Polyethers
- B01D71/522—Aromatic polyethers
- B01D71/5223—Polyphenylene oxide, phenyl ether polymers or polyphenylethers
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- 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
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- 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
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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
- C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
- C08G65/48—Polymers modified by chemical after-treatment
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- 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
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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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
- 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
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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
- 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]
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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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- 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]
-
- 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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/30—Cross-linking
-
- 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
- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
- C08J2371/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08J2371/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08J2371/12—Polyphenylene oxides
-
- 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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Abstract
本发明提供一种通过与产生酸性官能团的物质交联制备可用作离子导电膜的交联酸性聚合物的方法,如交联的磺化聚醚酮、磺化的聚砜、磺化的聚苯乙烯和其它酸性的聚合物。交联剂较好通过将酸基转化成酰亚胺官能团来结合到酸官能团上。由于N-H键的酸性,酰亚胺官能团补偿了由于酸基被占据而失去的酸性,从而保持了膜的导电性,同时有助于膜的强度和耐溶胀性。
Description
发明领域
本发明涉及一种适用于离子导电膜(ICM)的交联聚合物的制造方法。该方法通过ⅰ)与交联剂反应使具有酰基卤侧基的聚合物交联,所述的交联剂结合到两个或多个酰基卤基团上,或ⅱ)与交联剂反应使具有酰胺侧基的聚合物交联,所述的交联剂结合到两个或多个酰胺基团上。该交联剂较好结合到聚合物上产生酰亚胺基团。该酰亚胺基团用作提高聚合物离子导电能力的酸性基团。
发明背景
电化学装置(包括质子交换膜燃料电池、电解装置、氯碱分离膜、电池等)通常将离子导电膜用作固体电解质。在常规的电化学电池中,离子导电膜与阴极和阳极电极接触,并把阳极上形成的离子(如质子)传递给阴极,从而使电子流在连接这些电极的外部电路中流动。离子导电膜可含有聚合物电解质。质子或阳离子导电的离子导电膜可含有带阴离子或酸性官能团(如-CO2H,-SO3H或带酸性质子的其它基团)的聚合物电解质。
在常见的工业实践中,离子导电膜中一般使用未交联的磺化聚合物,如NafionTM(DuPont Chemicals,Inc.,Wilmington,DE),它由四氟乙烯和全氟乙烯基醚磺酸的共聚物制成。然而,市售的离子导电膜不能完全令人满意地满足燃料电池的性能要求。例如,在低当量时,NafionTM膜具有固有的结构脆弱性。一般不能得到厚度小于50微米的NafionTM膜。更薄的NafionTM膜需要增强,因此不能通过增加总厚度和增加膜的电阻来获得薄膜的目的。虽然更低当量的NafionTM膜可以获得更低的电阻,这些更低当量的膜在结构上也更脆弱。因此,仍不能消除增强的需要。
Buchi等在J.Electrochem.Soc.,142(9),3044页(1995年9月)中揭示了一种通过磺化交联的聚烯烃-聚苯乙烯共聚物制成的质子交换膜。这种聚合物通过在聚合过程中加入二乙烯基苯进行交联。
美国专利5,438,082揭示了一种使用两步、两部分交联剂交联磺化芳族聚醚酮的方法。交联分子是双官能的,含有胺官能团和可交联的组分。交联剂经其胺官能团连接到聚合物上的磺酰氯,形成磺酰胺,这种磺酰胺基团是水解不稳定的基团。这种处理消耗离子导电的磺酸官能度。在改性聚合物流延成膜后,可交联的组分连接形成交联物。该文献没有揭示或暗示通过形成稳定但高度酸性的键(如酰亚胺键)来保持该膜酸性的交联剂。
美国专利5,468,574和WO97/19480(1997年5月29日公开)揭示了一些磺化的聚合物在加热时会在磺酸盐基团之间直接形成键。这些文献没有揭示使用任何交联剂。WO97/19,480强调这种方法需要消耗磺酸基,并导致损失膜的酸性。
发明概述
总之,本发明提供一种交联聚合物的制造方法。该方法包括如下步骤:A)通过与交联剂反应使具有酰基卤侧基的聚合物交联,所述的交联剂结合到两个或多个酰基卤基团上;或者B)通过与交联剂反应使具有酰胺侧基的聚合物交联,所述的交联剂结合到两个或多个酰胺基团上;在A)或B)中通过与交联剂结合形成的基团是高度酸性的。这种方法可通过用通式(JAOn)mZ表示的交联剂使具有用通式-AOnG表示的侧基的聚合物交联而进行,式中G是卤素,且J是-NH2,或者G是-NH2,且J是卤素,各个A分别为C、S或P,对于各个AOn来说,当A是C时,n=1,当A是S或P时,n=2,m>1,Z是多价连接基团,可以是聚合物、取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。交联剂较好结合到聚合物上形成酰亚胺基团。一种优选的交联剂用通式NH2SO2RSO2NH2表示,式中R是取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团;R最好是-(CF2)4-。交联剂可在聚合物流延成膜之前或之后加入。如果在聚合物流延成膜之前加入交联剂,可以在聚合物流延成膜之前或之后引发交联步骤。
在另一方面,本发明提供用本发明方法制得的交联聚合物。
在另一方面,本发明提供具有用如下通式表示的交联键的交联聚合物:
([聚合物骨架]-AOnNHAOn)mZ
式中各个A分别为C、S或P,对于各个AOn来说,当A是C时,n=1,当A是S或P时,n=2,m>1,Z是多价连接基团,可以是聚合物、取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。
在另一方面,本发明提供具有用如下通式表示的交联键的交联聚合物:
([聚合物骨架]--SO2 NHSO2RSO2NHSO2--[聚合物骨架]
式中R的定义如上所述。
在另一方面,本发明提供具有用如下通式表示的交联键的交联聚合物:
([聚合物骨架]--SO2 NHSO2--[聚合物骨架]。
在另一方面,本发明提供由双官能交联剂制成的交联聚合物。该双官能交联剂具有一个与聚合物连接形成酸性官能团(较好酰亚胺)的官能团和第二个将交联剂相互连接的基团。
在另一方面,本发明提供由本发明方法制得的离子导电膜。
本领域中没有揭示且由本发明提供的内容是一般可用于用交联剂交联酸性聚合物的方法,如通常用于离子导电膜中的方法。上述的交联剂结合到酸性官能团上,但通过产生新的酸性官能团仍保留部分或所有聚合物的酸性。更具体地说,现有技术没有描述在与酸性聚合物结合时产生酰亚胺官能团的交联剂。另外,现有技术没有描述这种可在聚合物流延成膜之前或之后使用的方法。
在本申请中:
“酰胺”是指碳酰胺、磺酰胺或磷酰胺;
“酰亚胺”是指用如下通式表示的二价官能团:
-AOn-NH-AOn-式中各个A分别选自C、S或P,对于各个AOn来说,当A为C时,n=1,当A为S或P时,n=2;或用下式表示的任何含有除去氮上质子后产生的阴离子的盐:
-AOn-N-[M+]-AOn-式中M+是任何阳离子。
“杂原子官能团”是指含有杂原子(如O、N、S、P等)的基团。上述的杂原子可以取代烷基或芳基,而不影响所需的产物。例如,该杂原子官能团可以是醚、呋喃、吡咯等;
“取代的”是指被不影响所需产物的常见取代基取代。例如,上述的取代基可以是烷基、烷氧基、芳基、苯基、卤素(F、Cl、Br、I)、氰基、硝基等。
本发明的优点是通过产生氧化和水解稳定的交联键且不损失酸性官能团来提供交联的离子导电膜。本发明的另一优点是提供流延后交联膜(包括市售的膜)的方法。
优选实施方式的详细描述
本发明提供一种交联聚合物的制造方法。该方法包括如下步骤:A)通过与交联剂反应使具有酰基卤侧基的聚合物交联,所述的交联剂结合到两个或多个酰基卤基团上;或者B)通过与交联剂反应使具有酰胺侧基的聚合物交联,所述的交联剂结合到两个或多个酰胺基团上;在A)或B)中通过与交联剂结合形成的基团是高度酸性的。通过与交联剂结合形成的基团的pKa<5。这种方法可通过用通式(JAOn)mZ表示的交联剂使具有用通式-AOnG表示的侧基的聚合物交联而进行,式中G是卤素,且J是-NH2,或者G是-NH2,且J是卤素,各个A分别为C、S或P,对于各个AOn来说,当A是C时,n=1,当A是S或P时,n=2,m>1,Z是多价连接基团,可以是聚合物、取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。交联剂较好结合到聚合物上形成酰亚胺基团。A较好是C或S,A最好是S。
离子导电膜的高导电性要求膜中高的酸性部位的比率,即低的当量/酸基。不幸的是,低当量的聚合物一般可溶解于水和甲醇中。因此,这种聚合物不适用于许多电化学电池用途,如燃料电池。线型聚合物交联成三维网络大大地减少了这种膜在水和甲醇中的溶解度,减少了该膜的溶胀,减少了上述的膜相应于湿度改变的收缩和膨胀。
该交联剂较好结合到聚合物上,形成碳酰亚胺基或磺酰亚胺基。上述的交联剂较好形成至少一个二(磺酰)亚胺基。二(磺酰)亚胺基在强酸性条件和氧化条件下是稳定的,它本身是强酸,pKa一般小于5。当交联剂的结合形成二(磺酰)亚胺基时,由于聚合物上两个酸基被占据而失去的酸性可由交联剂上形成强酸基而得到补偿。因此,可以使预制的膜或市售的膜交联,而不会大量失去酸性。
合适的酸性或阴离子离子导电聚合物可用作原料,包括含有磺酸或羧酸侧基的聚合物。优选的聚合物包括聚醚醚酮(PEEK,购自American Hoechst Corp.,Somerville,NJ)、磺化聚醚醚酮(PEEK-SO3H)、聚砜(Amoco,Chicago,Ill.)、磺化聚砜、聚苯乙烯(购自Union Carbide Corp.,Danbury,CT)、磺化聚苯乙烯、聚苯醚(购自General Electric Co.,Pitsfield,Massachusetts)、磺化聚苯醚、磺化聚酰亚胺、NafionTM(DuPont Chemical Co.,Wilmington,DE)、上述聚合物的共聚物。上述聚合物的接枝共聚物和上述聚合物的取代聚合物,特别包括氟化聚合物,如磺化的聚α,β,β-三氟苯乙烯。酸基可用任何合适的方法转化成酰基氯基团,包括与亚硫酰氯反应。未磺化的聚合物可用任何合适的方法转化成带磺酰氯基团的聚合物。未磺化的芳族聚合物可用氯磺酸处理来将其直接转化成带磺酰氯基团的聚合物。
合适的交联剂包括任何与两个或多个酰基卤基团结合的分子。该交联剂较好结合到聚合物上,形成酰亚胺基团。优选的交联剂含有两个或多个酰胺基团,特别是碳酰胺或磺酰胺基团。交联剂可包括NH3、NH4OH以及通式为(NH2AOn)mZ的交联剂,式中每个A分别为C、S或P,对于各个AOn来说,当A是C时,n=1,当A是S或P时,n=2,m>1,Z是多价连接基团,可以是聚合物、取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。A较好是C或S,最好是S。优选的交联剂是NH4OH和通式为NH2SO2RSO2NH2的交联剂,式中R是取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。说明性的交联剂是NH2SO2CF2CF2CF2CF2SO2NH2、NH2C(O)CF2CF2CF2CF2C(O)NH2和NH2SO2C6H2Cl2SO2NH2。交联可用任何合适的方法进行。或者可将酰胺基团与酰基卤基团的位置交换。在这种情况下,带酰胺侧基的聚合物可与结合到两个或多个酰胺基团的交联剂一起使用。交联剂较好含有能与聚合物反应形成碳酰亚胺或磺酰亚胺官能团的酰基卤基团。交联剂和聚合物最好形成至少一个二(磺)酰亚胺官能团。交联剂可用通式(XAOn)mZ表示,式中X是卤素,较好是氯,每个A分别为C、S或P,对于各个AOn来说,当A是C时,n=1,当A是S或P时,n=2,m>1,Z是多价连接基团,可以是聚合物、取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。A较好是C或S,最好是S。最优选的交联剂包括通式为XSO2RSO2X的交联剂,式中X是卤素,较好是Br或Cl,最好是Cl,且R是取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。
也可使用具有聚合物连接官能团和交联剂连接官能团的双官能交联剂。聚合物连接基团连接到聚合物上按上述与交联剂相同的方式形成酸性官能团,较好酰亚胺官能团。交联剂连接官能团提供交联剂相互之间的连接、或同时使交联剂连接到聚合物上,或较好然后使交联剂连接到聚合物上。第二官能团可以是任何适于在交联剂分子间形成键的官能团,包括烯键类不饱和键,如三氟乙烯基醚、三氟苯乙烯、(甲基)丙烯酸酯、乙烯基肉桂酸、环氧化物、异氰酸酯、硅烷,如二烷氧基硅烷、三烷氧基硅烷、三氯硅烷或任何合适的其它官能团。第二官能团的反应可以是能量活化的,如光聚合或热聚合。第二官能团可以在反应前或反应过程中加入催化剂或引发剂来加以活化或加强。
交联剂和聚合物可以在无水条件、在聚合物流延成薄膜之前或之后进行混合。该混合物可以在非质子溶剂中制备,但也可以在没有溶剂的情况下制备。如果将各组分预混合,可以在混合物流延成薄膜之前或之后活化交联反应。为了保护酰基卤基团,在交联反应之前应注意排除水及其它能与酰基卤基团反应的物质。酰基卤-酰胺间的反应可以通过施加合适的碱(较好包括三烷基胺、吡啶或NaOH)进行活化。施加和活化交联剂(例如加入碱)可同时完成或分两步进行。混合和成膜可用任何合适的方法进行。
反应后,未反应的酰基卤官能团可用水或稀NaOH溶液水解。形成的聚合物可转化成布朗斯台德酸或通过阳离子交换转化成任何阳离子的盐。可以使用任何的阳离子,包括H+(假定是布朗斯台德酸)、金属阳离子和有机阳离子(如烷基铵阳离子)。碱性金属阳离子(如Li+、Na+、K+等)的盐是优选的,可制成可用作电池电解质的膜。转化成酸的形式是最优选的。该聚合物可通过与硝酸进行交换转化成酸。
在一个优选的实施方式中,由PEEK-SO2Cl或聚砜-SO2Cl与交联剂NH2SO2CF2CF2CF2CF2SO2NH2的混合物的四氢呋喃溶液流延成均匀的薄膜。PEEK-SO2Cl或聚砜-SO2Cl由PEEK或聚砜的氯磺化制得。将上述的膜浸入碱性溶液(如三乙胺或NaOH水溶液)使磺酰胺与磺酰氯之间反应,形成强酸二(磺酰)亚胺。另外,将没有与交联剂反应的磺酰氯基团水解成磺酸基。该反应表示如下:
形成的薄膜一般不溶解于甲醇,在水中的溶胀度较低,当在水中浸泡过夜时一般重量增加40%。这些交联膜的质子导电性是高的,一般在室温下为0,02-0.06S/厘米,接近于未交联膜的导电性。本发明用于制备或改良强度和离子导电性较高的离子导电材料,如电化学电池中所用的离子导电膜。本发明的目的和优点用如下的实施例作进一步的说明,但应当认为这些实施例中所用的具体材料及其用量以及其它条件和细节不应本发明构成不适当的限制。
实施例
如果没有其它说明,本申请中所用的试剂和设备都通过Aldrich ChemicalCo.,Milwaukee,WI得到。
在本发明的实验中,通过将二甲基甲酰胺(DMF)、N-甲基吡咯烷酮(NMP)或环戊酮溶液倒在玻璃或硅基板上流延成薄膜,然后先在室温下干燥,再在100℃下干燥。在本发明的实验中,吸水能力按如下方法测量:先将试样浸在水中,直到重量不再增加为止。记录最大重量。如果没有另作说明,水是室温下的水。然后将该试样放在100℃和0.1乇的条件下真空干燥24小时,再进行称重。吸水能力按湿重与干重之差除以干重计算,记录为百分数。本申请中所用的导电性试验依据T.Zawodzinski等,J.Phys.Chem.,1991,95,6040中公开的试验。试验前,将待测的膜放在去离子水中煮沸1小时。将该膜安装在电池中,室温下浸入水中,在100kHz-10Hz的频率范围、0V DC和100mV AC的条件下用阻抗谱仪测量膜阻抗的欧姆(实)分量和电容(虚)分量。产生虚阻抗对实阻抗的图(阻抗图,即Nyquist图),提供可外推到零电容的曲线。测量零电容处的欧姆电阻。由测得的电阻值计算导电率(S/厘米)以及电池常数和膜厚度。
实施例1制备磺化聚醚醚酮(PEEK-SO3H):
在500毫升特氟隆密封的玻璃瓶中加入30克聚醚醚酮(PEEK,购自HoechstAG,Frankurt,Germany)和400毫升浓硫酸(100-102%),制备一系列溶液。将这些玻璃瓶密封,室温下放在机械振荡机上振荡10至190小时之间不同的时间。磺化度随时间的增加而增加。将所得的粘性红色溶液倒入4升搅拌的冰水混合物中。收集沉淀物,捣碎成细粉末,用水洗涤至洗涤液呈pH中性为止。然后将白色的聚合物粉末放在40℃的真空(0.1乇)下干燥24小时。
这些聚合物(PEEK-SO3H)可溶解于DMF、NMP和环戊酮。在醇和热水中的溶解度随磺化度的增加而增加。这些膜的吸水能力为40%-5000%,随磺化度的增加而增加。该膜的室温导电率为0.01-0.06S/厘米,随磺化度的增加而增加。由PEEK-SO3H的溶液可流延成透明、独立(free standing)的薄膜。磺化度高的湿膜具有高的导电率,但机械强度差;而磺化度低的湿膜具有良好的机械强度,但导电率很差。
实施例2制备聚醚醚酮的磺酰氯(PEEK-SO2Cl);
将10克磺酸(PEEK-SO3H,按实施例1中所述的方法制得,磺化190小时)和80毫升亚硫酰氯加入一个250毫升圆底烧瓶。通氮下将该混合物回流12小时,形成粘性均相的溶液。然后将该混合物倒入500毫升搅拌的冰水混合物中。收集黄色的沉淀,捣碎成粉末,用大量的水洗涤,直到洗涤液呈pH中性为止。然后用甲醇将此聚合物洗涤两次,放在40℃(的真空(0.1乇)下干燥24小时。产率:9.8克(93%)。
该聚合物(PEEK-SO2Cl)可溶解于DMF、NMP、环戊酮、二氯乙烷、THF,但不溶解于醇和水中。由PEEK-SO2Cl溶液可制成透明独立的膜。该膜可用稀氢氧化钠溶液水解,然后经与硝酸交换转化成磺酸形式。水解后的膜在室温下的导电率为0.060S/厘米。虽然水解的膜具有高的导电率,但它在冷水中明显溶胀,且溶解于沸水中。
实施例3制备PEEK-SO2Cl的另一种方法:
在一个500毫升圆底烧瓶中加入300毫升氯磺酸。在氮气氛下加入30克PEEK。将此混合物搅拌2小时。然后将所得的微红色溶液倒入4升搅拌的冰水混合物中。收集沉淀,捣碎成粉末,用水洗涤,直到洗涤液呈pH中性为止。然后用甲醇将此聚合物洗涤两次,放在40C的真空(0.1乇)下干燥24小时。产率:35克(89%)。
如实施例2所述,该聚合物(PEEK-SO2Cl)可溶解于DMF、NMP、环戊酮、二氯乙烷、THF,但不溶解于醇和水中。由这些溶液可制成透明独立的膜。该膜可用稀氢氧化钠溶液水解,然后经与硝酸交换转化成磺酸形式。水解后的膜在室温下的导电率为0.060S/厘米。该膜在冷水中明显溶胀,且溶解于沸水中。
实施例4用NH2SO2C6H2Cl2SO2NH2交联PEEK-SO2Cl
在一个烧瓶中加入:0.00-0.20克(如表Ⅰ所示)NH2SO2C6H2Cl2SO2NH2(购自Sigma Chemical Co.,St.Louis,Missouri)、1.0克PEEK-SO2Cl(实施例2中制备)和9毫升环戊酮。形成均相的溶液。搅拌下,滴加0.6克Et3N。该溶液在2-20分钟内形成凝胶。将该凝胶过滤,用大量的水洗涤,然后用甲醇洗涤,再在在40℃的真空(0.1乇)下干燥24小时,得到白色固体。该交联的聚合物不溶解于常规的溶剂中,但在NMP和DMF中溶胀。表Ⅰ列出了不同交联密度的材料在沸水中的溶胀度。表Ⅰ也列出了不同材料的含氮量(用燃烧分析法测量,反映结合到最终聚合物中的交联剂量)。
表Ⅰ
实施例 | 4A | 4B | 4C | 4D | 4E |
PEEK-SO2Cl(克) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
交联剂(克) | 0.00 | 0.05 | 0.10 | 0.15 | 0.20 |
吸水能力,沸水(%) | 溶解 | 1480 | 82 | 27 | 21 |
N分析(%) | <0.1 | 0.40 | 0.71 | 1.10 | 1.35 |
实施例5
用NH2SO2(CF2)4SO2NH2交联PEEK-SO2Cl
在一个烧瓶中加入:0.00-0.20克(如表Ⅱ所示)NH2SO2(CF2)4SO2NH2(可用已知的方法合成,包括Hu,L.;DesMarteau D.D.;Inorganic Chem.1993,32,5007-5010中所述的方法)、1.0克PEEK-SO2Cl(实施例2中制备)和9毫升环戊酮。形成均相的溶液。搅拌下,滴加0.6克Et3N。该溶液在1-10分钟内形成凝胶。将该凝胶过滤,用大量的水洗涤,然后用甲醇洗涤,再在40℃的真空(0.1乇)下干燥24小时,得到白色固体。该交联的聚合物不溶解于常规的溶剂中,但在NMP和DMF中溶胀。表Ⅰ列出了不同交联密度的材料在沸水中的溶胀度。表Ⅰ也列出了不同材料的含氮量(用燃烧分析法测量,反映结合到最终聚合物中的交联剂量)。
表Ⅱ
实施例 | 5A | 5B | 5C | 5D | 5E |
PEEK-SO2Cl(克) | 1.0 | 1.0 | 1.0 | 1.0 | 1.0 |
交联剂(克) | 0.00 | 0.05 | 0.10 | 0.15 | 0.20 |
吸水能力,沸水(%) | 溶解 | 851 | 186 | 175 | 110 |
N分析(%) | 0.16 | 0.53 | 0.80 | 1.02 | 1.27 |
实施例6
制膜:PEEK-SO2Cl与NH2SO2C6H2Cl2SO2NH2
在一个烧瓶中加入1.0克PEEK-SO2Cl(按实施例2制备)、9毫升环戊酮和100毫克NH2SO2C6H2Cl2SO2NH2(购自Sigma Chemical Co.,St.Louis,Missouri)。形成均相的溶液。搅拌下滴加0.3克Pr3N,然后将此溶液迅速流延到一块平的玻璃盘上。让其干燥过夜后,将该盘子放入水中,从玻璃上剥离形成的膜。将该膜放在5%氢氧化钠水溶液中水解12小时,然后在20%硝酸中交换两次达1小时。然后在50℃下将该膜放在30%甲醇和70%水的混合液浸泡30分钟。于是,该膜变成透明的薄膜。然后将膜放在去离子水中交换几次。该膜不溶解于常规的溶剂,但在水中有点溶胀。该膜在沸水中的吸水能力为163%,比未交联材料的无穷大(即溶解)小。该膜在冷水中的吸水能力为40%,比未交联材料的5000%小。室温下测得的导电率为0.06S/厘米。
实施例7制膜:PEEK-SO2Cl与NH2SO2(CF2)4SO2NH2
在一个烧瓶中加入1.0克PEEK-SO2Cl(按实施例2制备)、9毫升环戊酮和100毫克NH2SO2(CF2)4SO2NH2(可用已知的方法合成,包括Hu,L.;DesMarteauD.D.;Inorganic Chem.1993,32,5007-5010中所述的方法)。形成均相的溶液。搅拌下滴加0.3克Pr3N,然后将此溶液迅速流延到一块平的玻璃盘上。让其干燥过夜后,将该盘子放入水中,从玻璃上剥离形成的膜。将该膜放在5%氢氧化钠水溶液中水解12小时,然后在20%硝酸中交换两次达1小时。然后在50℃下将该膜放在30%甲醇和70%水的混合液浸泡30分钟。于是,该膜变成透明的薄膜。然后将膜放在去离子水中交换几次。该形成的膜不溶解于常规的溶剂,但在水中溶胀。该膜在沸水中的吸水能力为101%,比未交联材料的无穷大(即溶解)小。该膜在冷水中的吸水能力为30%,比未交联材料的5000%小。室温下测得的导电率为0.065S/厘米。
实施例8制膜:PEEK-SO2Cl与NH2SO2(CF2)4SO2NH2
在一个烧瓶中加入1.0克PEEK-SO2Cl(按实施例2制备)、9毫升环戊酮和100毫克NH2SO2(CF2)4SO2NH2(可用已知的方法合成,包括Hu,L.;DesMarteauD.D.;Inorganic Chem.1993,32,5007-5010中所述的方法)。将这样形成的均相溶液迅速流延到一块平的玻璃盘上。让其干燥过夜后,将该盘子放入三乙胺与5%环戊酮的溶液中浸24小时。将该膜放在5%氢氧化钠水溶液中水解12小时,然后在20%硝酸中交换两次达1小时。然后在50℃下将该膜放在30%甲醇和70%水的混合液浸泡30分钟。于是,该膜变成透明的薄膜。然后将膜放在去离子水中交换几次。该形成的膜不溶解于常规的溶剂,但在水中溶胀。该膜在室温下的吸水能力为40%。室温下测得的导电率为0.055S/厘米。
本领域中熟练技术人员清楚不超出本发明范围和原则的各种改进和变化。而且应当理解本发明不受上述说明性实施方式的不适当限制。
Claims (16)
1.一种交联聚合物的制造方法,其特征在于它包括选自步骤ⅰ)和ⅱ)的步骤:
ⅰ)通过与交联剂反应使具有酰基卤侧基的聚合物交联,所述的交联剂结合到一个或多个酰基卤基团上,产生一个或多个pKa<5的基团,
ⅱ)通过与交联剂反应使具有酰胺侧基的聚合物交联,所述的交联剂结合到一个或多个酰胺基团上,产生一个或多个pKa<5的基团。
2.如权利要求1所述的方法,其特征在于所述的交联剂结合到具有能形成用如下通式表示的酰亚胺基团的侧基的聚合物上:
-AOn-N-[M+]-AOn-式中各个A分别选自C、S或P,对于各个AOn来说,当A为C时,n=1,当A为S或P时,n=2,且M+是包括H+在内的任何阳离子。
3.如权利要求1-3中任一项所述的方法,其特征在于它包括步骤ⅰ),其中所述的交联剂选自氨;铵;NH2SO2RSO2NH2,式中R是取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团;NH2SO2(CF2)4SO2NH2;NH2SO2(C6H4Cl2)SO2NH2。
4.如权利要求1或2所述的方法,其特征在于它包括步骤ⅱ),其中所述的交联剂具有通式XSO2RSO2X,式中X是卤素,R是取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。
5.如权利要求1-3中任一项所述的方法,其特征在于它包括步骤ⅰ),且还包括如下步骤:
ⅲ)通过将具有酰基卤侧基的聚合物与结合到两个或多个酰基卤基团上的所述交联剂混合,形成可交联的混合物,
然后是任意次序的下述步骤:
ⅳ)形成混合物的薄膜,及
ⅴ)通过将所述可交联的混合物置于碱性环境中使所述的聚合物交联。
6.如权利要求1-3中任一项所述的方法,其特征在于它包括步骤ⅰ),且还包括下述顺序步骤:
ⅵ)形成所述具有酰基卤侧基的聚合物的薄膜,
ⅶ)通过在反应性条件下施加结合到两个或多个酰基卤基团上的所述交联剂,使所述的聚合物交联。
7.如权利要求1、2或4所述的方法,其特征在于它包括步骤ⅱ),且还包括如下步骤:
ⅷ)通过将具有酰胺侧基的聚合物与结合到两个或多个酰胺基团上的所述交联剂混合,形成可交联的混合物,
然后是任意次序的下述步骤:
ⅸ)形成所述可交联混合物的薄膜,及
ⅹ)通过将所述可交联的混合物置于碱性环境中使所述的聚合物交联。
8.如权利要求1、2或4所述的方法,其特征在于它包括步骤ⅱ),且还包括下述顺序步骤:
ⅹⅰ)形成所述具有酰胺侧基的聚合物的薄膜,
ⅹⅱ)通过在反应性条件下施加结合到两个或多个酰胺基团上的所述交联剂,使所述的聚合物交联。
9.一种交联聚合物的制造方法,其特征在于它包括通过与用通式(JAOn)mZ表示的交联剂反应使具有用通式-AOnG表示的侧基的聚合物交联的步骤,式中G是卤素,且J是-NH2,或者G是-NH2,且J是卤素,各个A分别为C、S或P,对于各个AOn来说,当A是C时,n=1,当A是S或P时,n=2,m>1,Z是多价连接基团,可以是聚合物、取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。
10.如权利要求9所述的方法,其特征在于所述的交联剂选自氨;铵;NH2SO2RSO2NH2,式中R是取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团;NH2SO2(CF2)4SO2NH2;NH2SO2(C6H4Cl2)SO2NH2。
11.如权利要求9所述的方法,其特征在于所述的交联剂具有通式XSO2RSO2X,式中X是卤素,R是取代或未取代的烷基、取代或未取代的芳基或取代或未取代的杂原子官能团。
12.如权利要求9-11中任一项所述的方法,其特征在于它还包括如下步骤:
ⅹⅲ)通过将具有侧基的聚合物与所述交联剂混合,形成可交联的混合物,
然后是任意次序的下述步骤:
ⅹⅳ)形成所述混合物的薄膜,及
ⅹⅴ)通过将所述可交联的混合物置于碱性环境中使所述的聚合物交联。
13.如权利要求9-11中任一项所述的方法,其特征在于它还包括下述顺序步骤:
ⅹⅵ)形成所述具有侧基的聚合物的薄膜,
ⅹⅶ)通过在反应性条件下施加所述的交联剂,使所述的薄膜交联。
14.如权利要求1或2所述的方法,其特征在于所述的交联剂含有与聚合物结合的官能团和与交联剂结合的官能团,还包括使与聚合物结合的交联剂分子结合在一起的步骤。
15.如权利要求1-14中任一项所述方法制得的交联聚合物。
16.具有用如下通式表示的交联键的交联聚合物:
[聚合物骨架]-SO2N-[M+]SO2-[聚合物骨架],式M+是包括H+在内的任何阳离子。
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- 1999-01-28 CA CA002331720A patent/CA2331720A1/en not_active Abandoned
- 1999-01-28 KR KR1020007012842A patent/KR100576563B1/ko not_active IP Right Cessation
- 1999-01-28 CN CN99806422A patent/CN1301191A/zh active Pending
- 1999-01-28 AU AU25645/99A patent/AU2564599A/en not_active Abandoned
- 1999-01-28 EP EP99905499A patent/EP1077758A1/en not_active Withdrawn
- 1999-01-28 WO PCT/US1999/001782 patent/WO1999061141A1/en active IP Right Grant
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CN103937019A (zh) * | 2014-05-09 | 2014-07-23 | 中北大学 | 一种聚砜阳离子交换膜的制备方法 |
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CN107004455A (zh) * | 2014-07-23 | 2017-08-01 | Cdp创新公司 | 含有磺酰胺钠或锂盐的新型聚合物、其制备方法及其作为电池电解质的用途 |
CN107001622A (zh) * | 2014-07-23 | 2017-08-01 | Cdp创新公司 | 含有接枝的双(磺酰基)亚胺钠或锂盐的新型聚合物、其制备方法及其作为电池电解质的用途 |
CN107004455B (zh) * | 2014-07-23 | 2019-07-16 | Cdp创新公司 | 含有磺酰胺钠或锂盐的新型聚合物、其制备方法及其作为电池电解质的用途 |
CN108878934A (zh) * | 2018-07-02 | 2018-11-23 | 天津农学院 | 一种锂离子树脂离子导电膜的制备方法 |
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Also Published As
Publication number | Publication date |
---|---|
JP4718010B2 (ja) | 2011-07-06 |
CA2331720A1 (en) | 1999-12-02 |
WO1999061141A1 (en) | 1999-12-02 |
EP1077758A1 (en) | 2001-02-28 |
AU2564599A (en) | 1999-12-13 |
JP2002516348A (ja) | 2002-06-04 |
US6090895A (en) | 2000-07-18 |
KR20010043654A (ko) | 2001-05-25 |
KR100576563B1 (ko) | 2006-05-08 |
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