EP0852071A2 - Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises - Google Patents

Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises

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Publication number
EP0852071A2
EP0852071A2 EP96943846A EP96943846A EP0852071A2 EP 0852071 A2 EP0852071 A2 EP 0852071A2 EP 96943846 A EP96943846 A EP 96943846A EP 96943846 A EP96943846 A EP 96943846A EP 0852071 A2 EP0852071 A2 EP 0852071A2
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EP
European Patent Office
Prior art keywords
phenylene
copoly
electrolyte according
polymer
acid
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.)
Withdrawn
Application number
EP96943846A
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German (de)
English (en)
Inventor
Rolf Mülhaupt
Torsten Zerfass
Holger Frey
Konstantin Ledjeff-Hey
Roland Nolte
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP0852071A2 publication Critical patent/EP0852071A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
    • 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
    • H01M8/1023—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon, e.g. polyarylenes, polystyrenes or polybutadiene-styrenes
    • 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
    • H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
    • 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
    • H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
    • 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
    • C08J2365/00—Characterised by the use of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Derivatives of such polymers
    • 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
    • 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 a polymeric solid electrolyte with a hydrophobic backbone which is at least partially functionalized by ionic groups.
  • Solid polymer electrolytes are ion-exchange membranes, which consist of polymers with ionic groups. They have high ionic conductivity and, in contrast to liquid systems, mechanical stability. They come in various applications, such as. B. ion exchangers, (water) electrolyzers, batteries or fuel cells are used.
  • the invention relates to polymer electrolytes which are used primarily for use in fuel cells and electrolysers.
  • perfluorosulfonated membranes such as Nafion (trademark of DuPont) has been state of the art for many years. Unfortunately, these materials are only available with defined parameters (thickness, ion exchange capacity) and are not thermoplastic or processable from solutions. Furthermore, the high manufacturing costs have a negative impact.
  • Membranes based on other fluoropolymers are described, for example, in US 4,469,579, US 4,940,525 and WO 94/03503. Furthermore, sulfonated poly (phenylene ethers) can be found in US 3,259,592, US 3,484,293 or US 3,528,858. In addition, membrane materials are based on aromatic Polyether ketones are known from EP 0 575 807 AI or EP 0 574 791 A2. Polymer electrolytes based on sulfonated poly (p-phenylene) s are described in WO 94/24717.
  • the sulfonated polymers with poly (p-phenylene) backbone described by WO 94/24717 must have solubilizing side chains because of their rigid structure and their high degree of crystallinity so that they can be processed.
  • the properties of the polymer solid electrolytes known hitherto result in particular from the special chemical constitution of the polymer molecules.
  • they In addition to a non-polar backbone, they have functional groups that can be dissociated ionically.
  • the charges generated in the presence of water and the hydrophobic backbone lead to phase separation in ion-rich and ion-depleted areas.
  • Proton-conductive channels filled with water are formed.
  • the aggregated ions act as physical crosslinking points for the polymer molecules. To this This creates a macroscopically elastic, thermally reversible, physical network.
  • US 3,376,235 describes a linear, sulfonated poly (p-phenylene) with 1 to 2 sulfonic acid groups per 10 phenylene rings.
  • Unsubstituted poly (p-phenylene) (PPP) is highly crystalline, infusible and extremely insoluble due to the rigid structure ("rigid rod”). It is chemically and thermally very stable, but can hardly be processed due to the properties mentioned.
  • the sulfonation according to US 3,376,235 consequently requires very drastic conditions (oleum, 1 to 50 hours reaction time at 25 to 200 ° C.). Dark brown, still insoluble sulfonated materials are obtained as products. Due to the insolubility, however, no membranes can be made from it.
  • the invention has for its object to develop polymeric solid electrolytes with a preferably hydrophobic backbone, which is at least partially functionalized by ionic groups, in such a way that no side chains or groups to be provided for further processing are required for the production.
  • the materials should also not be produced on the basis of the rigid-rod concept described in WO 94/24717.
  • the thermal and chemical stability properties of the polymers are to be improved.
  • the polymer to be developed should be particularly suitable for use as an electrolyte membrane in electrolysis devices or in fuel cells.
  • a polymeric solid electrolyte with a preferably hydrophobic backbone, which is at least partially functionalized by ionic groups, is developed in such a way that the backbone of the polymer has a copoly (m-phenylene) which contains at least 20 mol% m-phenylene Contains units and is of the following structure:
  • Rl to R8 are hydrogen, aryl, oxyaryl, thioaryl,
  • the invention is based on the surprising finding that, by incorporating m-phenylene units in PPP, a soluble and fusible poly (m-phenylene-co-p-phenylene) is obtained despite the absence of solubilizing side chains.
  • substitution with side chains is advantageously not absolutely necessary for processability in the new materials. Even without ring substitution, sulfonation and electrolyte production are possible in copolymers with predominantly m-linking of the repeating units.
  • the invention allows for the first time the synthesis of polymer electrolytes whose polymer molecules only have the ionic groups. The advantage of such systems over systems with longer side groups has already been found in WO 94/03503 for fluorinated materials.
  • the polymeric solid electrolytes of this invention consist of copoly (m-phenylene) s of structure (1) with at least 20 mol% m-phenylene units.
  • a degree of functionalization with ionically dissociable groups should preferably be greater than 0 and less than 1. This degree of functionalization is to be understood as the average number of ionic groups per repeating unit.
  • the ionic groups can be randomly distributed over the polymer or preferably bound to certain repeating units.
  • the copoly (m-phenylene) s can be random, alternating, segmented or of another order.
  • Statistically structured copoly (m-phenylene) s are advantageously suitable for use as polymer electrolytes. Furthermore, a method is described with which it is possible for the first time to synthesize such structured Colpoly (m-phenylene) s in a statistical arrangement.
  • the substituents Rl to R8 can be hydrogen, aryl, oxyaryl, thioaryl, sulfonaryl, carbonylaryl, Oxyaryloxyaryl, hydroxyl or ionically dissociable groups.
  • Preferred ionically dissociable groups are in particular sulfonyl (-S03H), carboxyl (-C00H) or phosphoryl (-PO (OH) 2).
  • the substituent pairs R2 / R3 or R3 / R4 and / or R5 / R6 or R7 / R8 can also be fused arylene rings.
  • the polymer electrolytes according to the invention basically have a copoly (m-phenylene) backbone with a hydrophobicity similar to that of the poly (tetrafluoroethylene) backbone from Nafion.
  • the polymeric solid electrolytes according to the invention have a thermally and chemically extremely resistant, highly hydrophobic backbone made of copoly (m-phenylene) s, which is functionalized by ionic groups. In addition to a high proton conductivity, they show very favorable swelling behavior, which is reflected in good mechanical stability even at about 100 ° C. In addition, the materials can be processed from solutions in dipolar aprotic solvents and are therefore accessible in any layer thickness. The abundance of Known from the literature, and in some cases very well studied phenyl coupling reactions, the copoly (m-phenylene) s could also be made available from inexpensive starting materials.
  • the invention also includes a method of manufacturing membranes from functionalized copoly (m-phenylene) s.
  • copoly (m-phenylene) s can be synthesized in two ways.
  • a copolymer (m-phenylene) without ionic groups can be provided with such groups. This is preferably done by sulfonation.
  • the ionic groups can already be present in the monomers during the polymerization.
  • the copoly (m-phenylene) s can be synthesized by a regioselective or at least predominantly regioselective coupling of bifunctional aromatics according to one of the following principles:
  • aromatics with more electronegative substituents X and Y are polymerized in the presence of a reducing agent.
  • Tetrakis (triphenylphosphine-palladium-O) is preferably used as the catalyst in concentrations of 0.1 to 0.6 mol%, but in particular in concentrations between 0.2 and 0.5 mol%, based on the boronic acid groups.
  • the reaction takes place in a boiling mixture between 1 and 12 hours.
  • the unsubstituted copoly (m-phenylene) s precipitate during the reaction because of their insolubility.
  • the formation of copolymers could be shown spectroscopically (IR and - 3 C solid-state NMR) and with the help of DSC.
  • coply (m-phenylene) that can be synthesized from 65% 3-bromophenylboronic acid and 35% 4-bromophenylboronic acid. Surprisingly, it is soluble in nonpolar solvents such as paraffins at about 180 ° C. and has a melting point of 210 ° C. In this way, an unsubstituted, meltable and soluble polyphenylene can be obtained for the first time.
  • ionically dissociable groups are not already present in the monomers, they can be introduced into the copoly (m-phenylene) s, preferably by sulfonation.
  • the polymer backbone or side groups are sulfonated.
  • Various sulfonation methods are known, such as the reaction with concentrated Sulfuric acid, oleum, a mixture of sulfuric acid and thionyl chloride, sulfur trioxide or treatment with chlorosulfonic acid.
  • the sulfonation conditions suitable for the respective copoly (m-phenylene) can be determined by series of tests with increasingly tougher conditions.
  • a process for producing a polymeric solid electrolyte is specified in such a way that the polymer is a copoly (m-phenylene) with the structure (I) mentioned above, which is sulfonated with the addition of a sulfonating agent. After the sulfonation has ended, the sulfonated copoly (m-phenylene) is dissolved in an organic solvent. The solution is then applied to a support on which the solvent is evaporated. With the addition of water, the film remaining on the support is then detached and swollen.
  • the copoly (m-phenylene) s of the above structure can preferably be sulfonated very quickly with the aid of chlorosulfonic acid in chloroform.
  • the ethanol present in chloroform as a stabilizer is first treated with an excess Chlorosulfonic acid reacted and the chloroform was distilled off.
  • chloroform obtained in the distillation, air-smoking and saturated with hydrogen chloride is used without further pretreatment.
  • the copoly (m-phenylene) is suspended in this chloroform and treated with vigorous stirring with a solution of chlorosulfonic acid in the same solvent. Reaction times in the range of seconds result.
  • aromatic rings of the polymer backbone (Ar) are sulfonated by chlorosulfonic acid (equation (1).
  • the aryl-substituted chlorosulfonic acid should in turn have a sulfonating effect and be able to react with another aromatic ring to form a SO 2 bridge (equation (3)).
  • Fig. 1 a, b, c FT-IR spectra of various copoly (m-phenylene) e, made from 65% 3-bromophenylboronic acid and 35% 4-bromophenylboronic acid
  • FIG. 1 shows the FT-IR spectra of the non-sulfonated copoly (m-phenylene) s (see FIG. 1 a), which can be produced with the aid of measure 1b described below.
  • Fig. Lb shows that sulfonated with measure 2 Copoly (m-phenylene) s and Figure lc the copoly (m-phenylene) s, which were extremely strongly sulfonated overnight with pure chlorosulfonic acid, depending on the wave number in the range from 2000 cm-1 to 600 cm-1 (KBr compacts).
  • the spectrum shows the sulfonation of the copoly (m-phenylene) s according to equation (1).
  • the spectrum (see FIG. 1c) of the strongly sulfonated sample shows two strong bands at 1302.4 cm -1 and 1167.8 cm- 1 . They correspond to the symmetrical and the asymmetrical vibration of the crosslinking SO 2 groups that have arisen according to equation (3).
  • the degree of sulfonation can be calculated from elementary analyzes (C, H, S determination).
  • the electrolyte membrane is produced according to the invention by dissolving the copoly (m-phenylene) functionalized by ionic groups in an organic solvent, preferably a dipolar aprotic solvent, applying it to a glass support and slowly evaporating the solvent. The resulting film is then detached from the base in water, wherein a swollen membrane is created,
  • Solid electrolyte membrane the following measures should preferably be taken:
  • the solution is stirred at room temperature for about 8 hours and 200 ml of 1N hydrochloric acid are added.
  • the initially cloudy becomes clear with vigorous stirring organic phase and a viscous aqueous and a clear organic phase protruding.
  • the organic phase can then be easily decanted. By rinsing with ether and decanting, residues of the product can be removed from the flask.
  • the combined organic phases are extracted with a total of 500 ml of 2N sodium hydroxide solution in portions of 200, 100, 100, 100 ml.
  • the boronic acid passes into the sodium hydroxide solution as boronate.
  • the sodium hydroxide solution is again washed with 150 ml of diethyl ether.
  • the solution is then to be cooled to 0 ° C., while 6N hydrochloric acid is added while cooling until a pH of 2 has been established.
  • the boronic acid precipitates in crystalline form and can be suctioned off after it has been left to stand. After drying in vacuo, 20 g (78% of theory) of crude product are obtained.
  • the boronic acids Before being used for the polymerization, the boronic acids must be purified by recrystallization. They are dissolved in as little diethyl ether as possible and precipitated by adding pentane and cooling to -78 ° C. After drying in vacuo, 14.5 g (57%) of pure 3-bromophenyl boronic acid or 15 g (59%) of pure 4-bromophenyl boronic acid remain.
  • the reaction mixture is poured into about 11 methanol after cooling and acidified with 6N hydrochloric acid while stirring. If the evolution of carbon dioxide does not begin immediately, water is added in portions of 50 ml until a brisk reaction begins. After the evolution of gas has subsided, the mixture is cooled to 0 ° C. for about 24 hours. The polymer collects on the bottom and is finally sucked off. The unsubstituted copoly (m-phenylene) s are insoluble in normal organic solvents. The cleaning can therefore only be done by washing. To do this, the polymer is mixed with large amounts of water and ethanol washed. Ethanol also serves as a mediator since the polymer is not wetted by water at all. Finally, it is dried in a vacuum at 70 ° C. for 12 hours. The yields are typically 90%.
  • copolymers with the aid of FT-IR spectroscopy (KBr compacts) and l 3 C-solid state NMR spectroscopy are shown.
  • the FT-IR spectra of various poly (m-phenylene-co-p-phenylene) s are shown in the range from 2000 cm -1 to 600 cm * 1 in FIG. 2, exemplary 13 C.
  • Solid-state NMR spectra are shown in Fig. 3. The spectra show, depending on the monomer ratio used, continuous changes and document the presence of copolymers.
  • chloroform 100 ml of chloroform are mixed with 5 ml of chlorosulfonic acid and the chloroform is then distilled off via a small Vigreux column.
  • the chloroform which is saturated with hydrogen chloride and fumes in the air, is used for sulfonation.
  • the yield is 320 mg of hygroscopic, sulfonated material which is soluble in dipolar aprotic solvents such as N, N-dimethylformamide or dimethyl sulfoxide with heating. It is light yellow.
  • the degree of sulfonation is calculated from the elementary analysis (C, H, S). This is the sum formula for the sulfonated material
  • FT-IR spectroscopy provides information on S0 3 groups and H 2 0.
  • x is the degree of sulfonation, ie the average number of sulfonic acid groups per repeating unit.
  • the carbon content x c (percentage by weight) provided by the elementary analysis is calculated as:
  • the elementary analysis also provides the hydrogen content X H (weight fraction). This is used to check the calculated values x and y. The hydrogen content is calculated from x and y and with the actually measured value was compared. It applies to XH:
  • a sample of a copoly (m-phenylene) according to Example 2b) which has been sulfonated with a reaction time of 30 seconds (degree of sulfonation 26.45%) is to be stirred for about 7 days with an excess of 0.1N sodium hydroxide solution. It is then filtered off and washed until neutral with distilled water, then with methanol and diethyl ether and then dried in vacuo. The material loses its light yellow color and changes to a gray powder. Based on the empirical formula C 6 H 4 . X (S0 3 Na) x * y H 2 0
  • An electrolyte membrane produced according to measure 4 is first equilibrated in IN sulfuric acid for 24 hours. The measurement is carried out in 1 N sulfuric acid in an apparatus consisting of two half cells with platinum electrodes separated by the membrane. Measurements are made with an alternating current with a frequency of 1 kHz. First the resistance is measured several times without a membrane and then several times with a membrane and the two mean values are formed. The installation resistance RMembrane of the membrane is then calculated by forming the difference Rmit - Rohne.
  • the resistance of the membrane is calculated
  • a comparison measurement with Nafion 117 provides a specific resistance of 8.5 ⁇ cm.
  • a piece of a membrane produced according to measure 4 is dried in a vacuum drying oven at 110 ° C. and 300 hPa for 30 minutes. The mass is 33.3 mg.
  • the membrane is then swollen in water for 30 minutes at room temperature.
  • the membrane is briefly freed of adhering water after removal from the water bath with a filter paper and quickly weighed. It then swells at 80 ° C for 20 minutes and then at 90 ° C for 30 minutes. Finally, it is dried again at 110 ° C and 300 hPa for 30 min. Then the mass is again 33.3 mg.
  • the specific values can be found in the following table. The water absorption is calculated in% of the dry weight. Temperature mass water absorption water absorption water absorption

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  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention concerne un électrolyte solide polymère à squelette hydrophobe, fonctionnalisé au moins en partie par des groupes ioniques. L'invention concerne en outre un procédé de production d'un polymère, ainsi qu'une application préférée. L'invention se caractérise en ce que le squelette du polymère présente un copoly(m-phénylène) contenant au moins 20 % en moles d'unités m-phénylène et dont la structure est (a), R1 à R8 désignant hydrogène, aryle, oxyaryle, thioaryle, sulfonaryle, carbonylaryle, oxyaryloxyaryle, hydroxyle ou des groupes dissociables par voie ionique.
EP96943846A 1995-09-21 1996-08-28 Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises Withdrawn EP0852071A2 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19535086A DE19535086B4 (de) 1995-09-21 1995-09-21 Verwendung von polymeren Festkörperelektrolyten sowie Verfahren zu deren Herstellung
DE19535086 1995-09-21
PCT/DE1996/001599 WO1997011099A2 (fr) 1995-09-21 1996-08-28 Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises

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EP0852071A2 true EP0852071A2 (fr) 1998-07-08

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EP (1) EP0852071A2 (fr)
JP (1) JPH11515040A (fr)
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JP5720097B2 (ja) 2009-01-20 2015-05-20 住友化学株式会社 メタフェニレン系高分子化合物及びそれを用いた発光素子
JP7092996B2 (ja) * 2018-04-05 2022-06-29 国立大学法人山梨大学 高分子電解質、その製造方法、それを用いた高分子電解質膜、触媒層、膜／電極接合体、及び燃料電池
CN109608625B (zh) * 2018-11-16 2020-06-26 中国科学技术大学 有机共轭聚合物荧光材料及其合成方法

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WO1997011099A3 (fr) 1997-06-26
DE19535086B4 (de) 2004-08-12
DE19535086A1 (de) 1997-03-27
WO1997011099A2 (fr) 1997-03-27
JPH11515040A (ja) 1999-12-21

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