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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
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
  • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
• • 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
  • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
  • B01D71/441—Polyvinylpyrrolidone
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/52—Polyethers
  • B01D71/522—Aromatic polyethers
  • B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
  • B01D71/68—Polysulfones; Polyethersulfones
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
  • B01D71/06—Organic material
  • B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
  • B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • 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
  • C08G75/02—Polythioethers
  • C08G75/0204—Polyarylenethioethers
  • C08G75/0286—Chemical after-treatment
  • C08G75/0295—Modification with inorganic compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1025—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • 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
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1034—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having phosphorus, e.g. sulfonated polyphosphazenes [S-PPh]
• • 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. in situ polymerisation or in situ crosslinking
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/28—Degradation or stability over time
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2325/00—Details relating to properties of membranes
  • B01D2325/30—Chemical resistance
• • 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
• • 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
  • C08J2381/00—Characterised by the use 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; Polysulfones; Derivatives of such polymers
  • C08J2381/02—Polythioethers; Polythioether-ethers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M2300/00—Electrolytes
  • H01M2300/0017—Non-aqueous electrolytes
  • H01M2300/0065—Solid electrolytes
  • H01M2300/0082—Organic 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 the field of polymer chemistry and relates to sulfonated polyarylene compounds, as can be used, for example, in ion exchange membranes in fuel cells or other electrochemical processes or as low-fouling membranes for nano-, ultrafiltration or microfiltration or reverse osmosis, and to a process their manufacture and use.
• the acidic polymer electrolyte fuel cell is characterized by a high power density and a favorable power to weight ratio.
• Membranes of poly (perfluoroalkylsulfonic acids) such as B. Nafion ® (DuPont) apply z.
• B. Nafion ® DuPont
• a higher operating temperature is desirable, since the electrode kinetics are favorably influenced, catalyst poisons such as carbon monoxide desorb faster and cooling requires less effort (C. Wieser, Fuel CeIIs 4, 245 (2004)).
• the poly (perfluoroalkylsulfonic acids) have a high Methylene permeability, which excludes them for use in DMFC (direct methanol fuel cell).
• sulfonated polyaryl compounds are intensively studied.
• poly (ether ketones) PEK, PEEK
• poly (ether sulfones) PES, PEES
• Other high performance sulfonated polymers such as polyimides have also been studied (N.Cornet et al., J.New Mater. Electrochem., Syst., 3, 33-42 (2000)).
• these are not suitable for use as fuel cell membranes in terms of their chemical stability (G. Meier et al., Polymer 47, 5003 - 5011 (2006)).
• Polymeric sulfonated aromatic side-chain fuel cell membranes have also been described.
• the aim is to support the microphase separation between the hydrophobic main chain and hydrophilic elements (sulfonic acid groups). It is expected that the swelling of the membranes in water will be minimized by the introduced spacers between polymer backbone and sulfonic acid group.
• Lafitte et al. have reacted a bisphenol-A based polysulfone with the cyclic anhydride of 2-sulfobenzoic acid and other electrophiles in a two-step and multi-step reaction (B. Lafitte et al., Macromol Rapid Commun., 23, 896-900 (2002) and ibid 26, 1464-1468 (2005)).
• the polymer is activated by reaction with butyllithium.
• the second stage involves the reaction of the activated polymer with 2-sulfobenzoic anhydride or fluorobenzoyl chloride. The latter is reacted in a further step in a nucleophilic reaction with a Hydroxyarylsulfonkla.
• a disadvantage of this process is the sensitivity of the reactants (BuLi, activated polymer) to impurities (eg water, oxygen, carbon dioxide) and the associated side reactions and the poor control of the degree of sulfonation, as well as the relatively high price for butyllithium.
• Gieselmann et al. have side groups sulfonated polybenzimidazoles (M. Gieselman et al., Macromolecules, 25, 4832-4834 (1992)) to improve the solubility of these polymers.
• the modification was carried out by alkylation of the NH nitrogen of Imidazolringes in a two-stage reaction 1.) deprotonation of the NH nitrogen with a strong base (LiH) and subsequent reaction with 1, 3-propanesultone or Benzylbromidsulfonklare.
• the object of the present invention is to provide hydrolysis- and thermostable, sulfonated polyarylene compounds having a defined degree and degree of sulfonation, from which membrane materials having improved resistance to hydrolysis can be prepared, and to provide a simple and cheaper production method therefor.
• the object is achieved by the invention specified in the claims.
• Advantageous embodiments are the subject of the dependent claims.
• the sulfonated polyarylene compounds according to the invention are synthesized according to at least one of the general formulas (I) - (IV),
• Gi is a group with electron acceptor properties
• G 2 is an ether and / or sulfide and / or keto and / or sulfone and / or phenylphosphine oxide and / or sulfoxide group and
• Ri, R2, R3, R4 are substituents or Ri to R 4 is hydrogen or at least one radical Ri to R 4 is not hydrogen and this is a substituent, and
• Ar one or more mononuclear and / or polynuclear aromatics and / or one or more biphenyls,
• Gi is a sulfone group and / or a keto group and / or a phenylphosphine group.
• y> 2 and more preferably y> 4.
• Ar is at least one phenyl radical and / or at least one naphthyl radical.
• the polyarylene compounds predominantly have a block structure. Furthermore, it is also advantageous if the polyarylene compounds have a random or a pure block structure.
• aromatic groups "Ar" as side chain are directly covalently bound to a mono- or polynuclear aromatic of the main chain.
• a membrane material consists of at least one sulfonated polyarylene compound.
• At least one further polymer of aromatic monomer units via sulfide and / or sulfoxide and / or sulfone and / or ether and / or keto and / or methylene and / or isopropyl and / or hexafluoroisopropyl and / or phenylphosphine oxide and / or imidazole and / or oxazole and / or thiazole and / or quinoxaline and / or quinoxazole groups.
• aromatic monomer units are substituted.
• At least single aryl-substituted 1,4-dihydroxybenzenes / hydroquinones and / or 1,4-dihydroxynaphthalenes are polymerized as aryl monomers having an aromatic group "Ar” together with dihaloaromatic compounds to give aryl compounds and subsequently at least sulfonic acid groups the aromatic groups "Ar" bound.
• the aryl monomers used are phenylhydroquinone and / or naphthylhydroquinone and / or anthracenylhydroquinone and / or 2,5-diphenylhydroquinone and / or biphenylylhydroquinone and / or 2,5-bis-biphenylylhydroquinone and / or tetraphenylhydroquinone and / or 1,4-dihydroxyquinone 2-phenylnaphthalene and / or 1, 4-dihydroxy-2-naphthylnaphthalene used.
• the aryl monomers are polymerized into aryl polymers having aromatic groups "Ar" as the side chain in solution.
• the aryl monomers are polymerized into aryl polymers having aromatic groups "Ar" as a side chain in melt.
• difluorodiphenylsulfone and / or difluorobenzophenone and / or bis (4-fluorophenyl) phosphine oxide and / or bis (4-fluorobenzoyl) benzene or dichlorodiphenyl sulfone and / or dichlorobenzophenone are used as dihalogenoaromatics.
• aryl polymers having aromatic groups "Ar” as side chain are sulfonated by adding the polymers to give a sulfonating agent. It is advantageous if the aryl polymers are dissolved with aromatic groups "Ar” as the side chain in an inert solvent and sulfonated with a sulfonating agent, being particularly advantageous when sulfonating as sulfuric acid or oleum or chlorosulfonic acid or
• Chlorosulfonkladish Trimethylsilylester or acetyl sulfate or a SO 3 -Triethylphosphit- adduct is used. It is furthermore of particular advantage if the sulfonating agent is sulfuric acid and the sulfonation is carried out at room temperature and during a reaction time of 1 to 8 hours, advantageously over a period of 2 to 4 hours.
• the sulfonating agent is used dissolved in an inert solvent, wherein advantageously chloroform or dichloromethane or dichloroethane or tetrachloroethane is used as the solvent.
• the sulfonating agent used is chlorosulfonic acid trimethylsilyl ester.
• a membrane is produced from the sulfonated polyarylene compounds.
• the sulfonated polyarylene compounds are used as membrane material.
• they are used as membrane material for ion exchange membranes for fuel cells or other electrochemical processes or as Nanofiltration membrane or used as an ultrafiltration membrane or as a microfiltration membrane or as a reverse osmosis membrane.
• Dihydroxybiphenyl is significantly higher compared to PEEK and PES.
• the production process according to the invention is very cost-effective, since commercial monomers can be used.
• free bisphenols and dichloroaromatics can also be used, which also makes the polymers according to the invention significantly cheaper.
• a reaction temperature of 190 - 200 0 C must be selected.
• Membranes of the sulfonated polyarylene compounds according to the invention have, compared to the prior art, in particular Nafion, a significantly lower methanol permeability, without deteriorating other properties, which predestined these membranes, especially for use in the DMFC.
• M w molar mass in (g / mol) (weight average)
• NMR spectra were recorded to determine the degree of sulfonation and the location of sulfonation. Representative are the spectra of the sample from Example 4 listed.
• FIG. 1 1 H-NMR spectra (aromatic region) for example 4, FIG.
• the monomers are dissolved and the reaction solution is mixed with 24.88 g (180 mmol) of anhydrous potassium carbonate.
• the reaction mixture is heated to 175 ° C and held for 24 h at this temperature.
• the solution is filtered to separate any undissolved components (salts) and then the polymer is precipitated in 2-propanol.
• the polymer is dissolved in chloroform and any undissolved constituents are separated by filtration.
• the polymer is in 2-propanol Like, carefully washed first with 2-propanol and then with methanol and dried in vacuo at 80 0 C to constant weight.
• the sulfonation is carried out by dissolving the polymer in concentrated sulfuric acid (96-98%) and stirring for 4 hours at 25 ° C.
• the sulfonation product is precipitated by pouring the sulfuric acid solution into cold water. After thorough washing with cold water (to pH 7 of the wash water), the product is dried in vacuo at 80 0 C to constant weight. The degree of sulfonation was determined by titration.
• the reaction mixture is heated to 175 ° C and held for 24 h at this temperature. After cooling to room temperature, the solution is filtered to separate any undissolved components (salts) and then the polymer is precipitated in 2-propanol. The polymer is dissolved in chloroform and any undissolved constituents are separated by filtration. The polymer is precipitated in 2-propanol, carefully washed first with 2-propanol and then with methanol and dried in vacuo at 80 0 C to constant weight.
• the sulfonation is carried out by dissolving the polymer in concentrated sulfuric acid (96-98%) and stirring for 4 hours at 25 ° C.
• 6,6115g (30.3 mmol) of 4,4-difluorobenzophenone ⁇ , 9,917g (30 mmol) of 2,5-bis trimethylsiloxybiphenyl (phenylhydroquinone-bis-trimethylsilyl ether) may be under the exclusion of moisture in a 100 ml 3-neck round bottom flask was weighed and mixed with 50 ml of anhydrous N-methyl-2-pyrrolidone. Under a slight stream of argon, the monomers are dissolved and the reaction solution is mixed with 4.146 g (30 mmol) of anhydrous potassium carbonate. The reaction mixture is heated to 175 ° C and held for 24 h at this temperature.
• the solution is filtered to separate any undissolved components (salts) and then the polymer is precipitated in 2-propanol.
• the polymer is dissolved in chloroform and any undissolved constituents are separated by filtration.
• the polymer is precipitated in 2-propanol, carefully washed first with 2-propanol and then with methanol and dried in vacuo at 80 0 C to constant weight.
• the sulfonation is carried out by dissolving the polymer in concentrated sulfuric acid (96-98%) and stirring for 4 hours at 25 ° C.
• the sulfonation product is precipitated by pouring the sulfuric acid solution into cold water. After thorough washing with cold water (to pH 7 of the wash water), the product is dried in vacuo at 80 0 C to constant weight.
• the hydrolytic stability of the sulfonated material was tested by treating the membranes prepared according to Example 5 in water or dilute aqueous mineral acids (2% HCl) at 135 ° C for a period of 168 hours. When comparing the 1 H-NMR spectra of the samples before and after the thermal treatment, there were no differences.

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• 2006
  • 2006-07-28 DE DE102006036496A patent/DE102006036496A1/de not_active Withdrawn
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