WO2000066254A1 - Stufenweise alkylierung von polymeren aminen - Google Patents
Stufenweise alkylierung von polymeren aminen Download PDFInfo
- Publication number
- WO2000066254A1 WO2000066254A1 PCT/EP2000/003914 EP0003914W WO0066254A1 WO 2000066254 A1 WO2000066254 A1 WO 2000066254A1 EP 0003914 W EP0003914 W EP 0003914W WO 0066254 A1 WO0066254 A1 WO 0066254A1
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- Prior art keywords
- polymer
- acid
- polymers
- groups
- membranes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
- C25B13/08—Diaphragms; Spacing elements characterised by the material based on organic materials
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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
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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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
- B01D71/76—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
-
- 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
- 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
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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
- 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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- 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
- H01M8/20—Indirect fuel cells, e.g. fuel cells with redox couple being irreversible
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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
- H01M8/1009—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]
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Definitions
- the invention relates to:
- Acid-base blends / acid-base blend membranes obtainable by process (6), it being possible for the blend / blend membranes to be additionally covalently crosslinked.
- tertiary amine and quaternary ammonium salt are formed in addition to secondary amine.
- Mixtures of low molecular weight primary, secondary and tertiary amines can be separated from one another, for example, by distillation.
- primary, secondary and tertiary amino groups can be present at the same time after the reaction on a macromolecule.
- secondary or tertiary polymeric amines cannot be produced in a targeted manner from primary polymeric amines. This technical problem is solved by this invention.
- lithiated polysulfone for example lithiated polysulfone (Guiver, MD; Robertson, GP: Chemical Modification of Polysulfones: A Facile Method of Preparing Azide Derivatives From Lithiated Polysulfone Intermediates, Macromolecules 28, 294-301 (1995)) and subsequent reduction the azide group with sodium borohydride to the amino group (Guiver, MD; Robertson, GP; Foley, S .: Chemical Modification of Polysulfones II: An Efficient Method for Introducing Primary Amine Groups onto the Aromatic Chain, Macromolecules 28, 7612-7621 (1995)).
- Tertiary amino groups can be introduced into polymers by allowing lithiated polymers to react with aromatic ketones, aldehydes or carboxylic acid esters containing tertiary amino groups (Kerres, J .; Ullrich, A .; Häring, Th .: Modification of engineering polymers with N-basic ones Groups and with ion exchange groups in the side chain, German patent application 198 36 514.4 from August 12, 1998) No reaction is known from the prior art with which secondary amino groups can be introduced into a polymer in a targeted manner, and no reaction is known from the prior art , with a polymer with primary amino groups Polymer with secondary amino groups and from this a polymer with tertiary amino groups can be produced.
- This invention makes it possible to obtain polymers which contain secondary amino groups and / or tertiary amino groups and / or quaternary ammonium groups, which can be obtained in stages from the polymer modified with primary amino groups.
- this invention makes it possible to obtain polymers which, in addition to tertiary amino groups which have been obtained by stepwise alkylation of the primary and secondary amino groups, also contain further functional groups which were introduced in one or more further reaction steps after the generation of the tertiary amino group .
- membranes made from the above-mentioned polymers and from other polymers which can be admixed become accessible.
- aminated polysulfone PSU dissolved in tetrahydrofuran which can be obtained using (Guiver, MD; Robertson, GP; Foley, S .: Chemical Modification of Polysulfones II: An Efficient Method for Introducing Primary Amine Groups onto the Aromatic Chain, Macromolecules 28, 7612-7621 (1995)) can be produced by n- Let butyllithium selectively deprotonate on the amino group to form the salt PSU-NH ⁇ Li + . If the salt PSU-NH "Li + is mixed with an equimolar amount of methyl iodide, the secondary polymeric amine PSU-NH-CH 3 is formed . This secondary polymeric amine can be dissolved in THF-
- the tertiary polymeric amine is prepared from the secondary polymeric amine by using a molar deficit of, for example, n- Butyllithium not all NHCH 3 groups deprotonated to NCH 3 ⁇ Li + , can be obtained after addition of the methyl iodide, polymers which, in addition to the tertiary groups N (CH 3 ) 2, also secondary amino groups NHCH 3 in the desired ratio N (CH3) 2 to NHCH 3 included.
- a molar deficit of, for example, n- Butyllithium not all NHCH 3 groups deprotonated to NCH 3 ⁇ Li + can be obtained after addition of the methyl iodide, polymers which, in addition to the tertiary groups N (CH 3 ) 2, also secondary amino groups NHCH 3 in the desired ratio N (CH3) 2 to NHCH 3 included.
- the tertiary PSU amine can be further converted to the quaternary ammonium salt using customary methods (Goerdeler, J .: Preparation of quaternary ammonium compounds, Houben-Weyl, Methods of Organic Chemistry, Volume XI / 2 nitrogen compounds II, Georg Thieme Verlag, Stuttgart, S. 591 f. (1958)).
- Fig. 1 shows the gradual alkylation of aminated PSU to the tertiary PSU amine
- Fig. 2 the quaternization of the tertiary PSU amine.
- the polymer containing the secondary and / or tertiary amino groups can now be modified with further functional groups.
- PSU containing secondary or tertiary amino groups can be modified by means of electrophilic substitution reactions with further functional groups.
- Fig. 3 shows the electrophilic sulfonation of PSU containing tertiary amino groups with concentrated sulfuric acid.
- Polymer containing tertiary amino groups can be metalated with organometallic reagents, the metalated polymer containing tertiary amino groups can be used with virtually all electrophiles, as described in (Guiver, MD: Aromatic Polysulfones Containing Functional Groups by Synthesis and Chemical Modification, Dissertation, Carletown University, Ottawa-Ontario, Canada (1987); Guiver, MD; Kutowy, O .; Apsimon, JW: Aromatic polysulfone derivatives and processes for their preparation, DE-Offen 36 36 854 AI (1987)) for only lithiated, non-aminated PSU, are brought to reaction.
- FIG. 4 shows the lithiation of tertiary PSU amine with subsequent reaction of the lithiated PSU containing tertiary amino groups with SO 2 Cl 2 to form the PSU, which also contains SO 2 Cl groups in addition to tertiary amino groups.
- the PSU amine sulfochloride can be hydrolyzed in a further step to the PSU amine sulfonic acid.
- a dipolar aprotic solvent for example dimethyl sulfoxide DMSO, sulfolane, N, N-dimethylformamide DMF, N, N - Dimethylacetamide DMAc, N-methylpyrrolidinone NMP.
- the dihaloalkane reacts with the tertiary amino groups with the simultaneous formation of quaternary ammonium groups and covalent crosslinking sites (Fig. 5).
- the acid-base polymer / the acid-base polymer membrane is brought into the acid form by aftertreatment in dilute mineral acid, that is to say the X "-" microions "are replaced by” macroions "of the acidic groups of the polymer, in addition to the covalent crosslinking of the Polymer still receive intra- and intermolecular ionic crosslinking of the acid-base polymer, which significantly increases the mechanical and thermal stability of the polymer.
- the diaminated PSU is dissolved in THF under argon. Then it is cooled down to -70 ° C. The solution is titrated with 2.5 M n-BuLi until the deep red color of the PSU-NH-Li + ion is formed. Then the 10 M n-BuLi solution is injected into the polymer solution. The solution is allowed to stir for 30 minutes. The methyl iodide is then injected into the solution. The solution becomes discolored. The solution is allowed to warm to room temperature and the triethylamine is injected to destroy excess methyl iodide. The mixture is heated to 40 ° C. and left to stir for 1 hour. Then the reaction solution is precipitated in 2 L of isopropanol.
- the mixture is stirred for 1 hour and the polymer precipitate is filtered off.
- the filter residue is slurried in 1 L of isopropanol and stirred for one day (24 hours).
- the mixture is then filtered again and the filter residue is kept in a drying cabinet in 1 L of water at 70 ° C. for 1 day in order to wash out amine residues from the polymer. It is filtered again and washed with water until the washing solution shows a neutral reaction.
- the polymer is dried to constant weight at 70 ° C in a vacuum drying cabinet.
- the diaminated PSU is dissolved in THF under argon. Then it is cooled down to -30 ° C. The solution is titrated with 2.5 M n-BuLi until the deep red color of the PSU-NH "Li + ion is formed. Then the 10 M n-BuLi solution is injected into the polymer solution. The solution is left to stir for 30 minutes The methyl iodide is then injected into the solution. The solution decolorises. The solution is allowed to warm to room temperature and the triethylamine is injected to destroy excess methyl iodide. The mixture is heated to 40 ° C.
- Tab. 1 shows the results of the elementary analysis of PSU (NH 2 ) 2 .
- the agreement between the calculated and experimental elementary analysis data is good.
- IR spectra of PSU (NH 2 ) 2 , PSU (NH (CH 3 ) 2 and PSU (N (CH 3 ) 2 ) 2 are shown in Fig. 6. They show significant differences Wavenumber range 3300 to about 3550 cm- 1 , the range of the NH stretching vibrations, so that the primary symmetrical and asymmetrical NH stretching vibrations occur in the primary PSU amine, while only a NH stretching vibration is naturally present in the secondary PSU amine tertiary PSU amine completely should have disappeared.
- an NH stretching vibration is significantly weakened compared to the IR spectrum of the secondary PSU amine. This indicates that there is only a small proportion of secondary amino groups in the tertiary PSU amine.
- Fig. 7 shows the thermogravimetry (TGA) curves of the three membranes listed in Tab. 2.
- TGA thermogravimetry
- the glass plate with the polymer film is allowed to cool and then placed in a water bath so that the polymer film detaches from the glass plate.
- the membrane is then after-treated for 24 h at 70-80 ° C in 10% sulfuric acid and then for 24 h at 60 ° C in water. The proton resistance of the membrane is then measured.
- Secondary and / or tertiary polymeric amines can be produced in a targeted manner from primary polymeric amines.
- the yields of the reaction are good; in the case of mixed polymeric amines according to the invention, the ratio between primary and secondary and between secondary and tertiary amino groups can be set in a targeted manner.
- Quaternary ammonium salts (anion exchange polymers and membranes) can be produced in a targeted manner from the tertiary polymeric amines thus obtained or crosslinked to the desired degree.
- polymeric amines according to the invention can, if desired, be reacted with polymers containing cation exchange groups to give acid-base blends.
- the acid-base polymers and acid-base polymer blends according to the invention can be covalently and ionically crosslinked at the same time. 9th words
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- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
- Conductive Materials (AREA)
- Polyethers (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
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Abstract
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Claims
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU18238/01A AU779428B2 (en) | 1999-04-30 | 2000-05-02 | Step-by-step alkylation of polymeric amines |
IL14620800A IL146208A0 (en) | 1999-04-30 | 2000-05-02 | Step-by-step alkylation of polymeric amines |
EP00938622A EP1175254A1 (de) | 1999-04-30 | 2000-05-02 | Stufenweise alkylierung von polymeren aminen |
BR0010170-2A BR0010170A (pt) | 1999-04-30 | 2000-05-02 | Alquilação gradual de aminas poliméricas |
KR1020017013910A KR100749156B1 (ko) | 1999-04-30 | 2000-05-02 | 중합체아민의 단계적 알킬화 |
JP2000615131A JP2002543244A (ja) | 1999-04-30 | 2000-05-02 | ポリマーアミンの段階的なアルキル化 |
CA002371967A CA2371967A1 (en) | 1999-04-30 | 2000-05-02 | Step-by-step alkylation of polymeric amines |
IL146208A IL146208A (en) | 1999-04-30 | 2001-10-29 | Stage alkylation and polymer amines |
US09/984,488 US7132496B2 (en) | 1999-04-30 | 2001-10-30 | Step-by-step alkylation of polymeric amines |
AU2005201750A AU2005201750A1 (en) | 1999-04-30 | 2005-04-27 | Step-by-step alkylation of polymeric Amines New Title: Crosslinked Acid-Base Membranes |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19919708A DE19919708A1 (de) | 1999-04-30 | 1999-04-30 | Stufenweise Alkylierung von polymeren Aminen |
DE19919708.3 | 1999-04-30 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US09/984,488 Continuation US7132496B2 (en) | 1999-04-30 | 2001-10-30 | Step-by-step alkylation of polymeric amines |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2000066254A1 true WO2000066254A1 (de) | 2000-11-09 |
WO2000066254A8 WO2000066254A8 (de) | 2002-05-30 |
Family
ID=7906422
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2000/003914 WO2000066254A1 (de) | 1999-04-30 | 2000-05-02 | Stufenweise alkylierung von polymeren aminen |
Country Status (12)
Country | Link |
---|---|
US (1) | US7132496B2 (de) |
EP (1) | EP1175254A1 (de) |
JP (2) | JP2002543244A (de) |
KR (1) | KR100749156B1 (de) |
CN (1) | CN1212177C (de) |
AU (1) | AU779428B2 (de) |
BR (1) | BR0010170A (de) |
CA (1) | CA2371967A1 (de) |
DE (1) | DE19919708A1 (de) |
IL (2) | IL146208A0 (de) |
WO (1) | WO2000066254A1 (de) |
ZA (1) | ZA200109818B (de) |
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WO2003034445A1 (en) * | 2001-10-11 | 2003-04-24 | Sony Corporation | Proton conductor, process for its production and electrochemical devices |
WO2003050169A2 (de) * | 2001-05-21 | 2003-06-19 | Haering Thomas | Kovalent vernetzte kompositmembranen |
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JP2015057484A (ja) * | 2000-05-19 | 2015-03-26 | ウンベルシテート シュトゥットガルト インスティチュート フュア ヘミシェ フェアファーレンステヒーク | 共有結合性およびイオン結合性架橋高分子および高分子膜 |
JP2012162722A (ja) * | 2000-05-19 | 2012-08-30 | Univ Stuttgart | スルフィナートアルキル化を介した共有結合架橋ポリマーおよびポリマー膜 |
KR100925846B1 (ko) * | 2000-05-19 | 2009-11-06 | 우니베르지테트 슈트트가르트 인스티투트 퓌어 헤마쉐 페어파렌스테히닉 | 설피네이트 알킬레이션에 의해 공유결합으로 가교된 폴리머 및 폴리머 막 |
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KR100815065B1 (ko) * | 2001-02-15 | 2008-03-20 | 스미또모 가가꾸 가부시키가이샤 | 방향족 중합체 포스폰산 유도체 및 이의 제조방법 |
WO2003050169A3 (de) * | 2001-05-21 | 2003-08-21 | Thomas Haering | Kovalent vernetzte kompositmembranen |
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JP2008171620A (ja) * | 2007-01-10 | 2008-07-24 | Fujitsu Ltd | アニオン交換型電解質組成物、固体電解質膜および燃料電池 |
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Also Published As
Publication number | Publication date |
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US20020103306A1 (en) | 2002-08-01 |
WO2000066254A8 (de) | 2002-05-30 |
KR100749156B1 (ko) | 2007-08-14 |
KR20020016779A (ko) | 2002-03-06 |
IL146208A (en) | 2008-11-26 |
US7132496B2 (en) | 2006-11-07 |
EP1175254A1 (de) | 2002-01-30 |
IL146208A0 (en) | 2002-07-25 |
AU779428B2 (en) | 2005-01-27 |
AU1823801A (en) | 2002-01-30 |
DE19919708A1 (de) | 2001-03-01 |
BR0010170A (pt) | 2002-01-15 |
JP2011026592A (ja) | 2011-02-10 |
ZA200109818B (en) | 2003-02-26 |
CN1212177C (zh) | 2005-07-27 |
JP2002543244A (ja) | 2002-12-17 |
CN1364098A (zh) | 2002-08-14 |
CA2371967A1 (en) | 2000-11-09 |
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