Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G75/00—Macromolecular compounds obtained by reactions forming a linkage containing sulfur with or without nitrogen, oxygen, or carbon in the main chain of the macromolecule
  • C08G75/20—Polysulfones
  • C08G75/23—Polyethersulfones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/18—Manufacture of films or sheets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
  • C08L81/06—Polysulfones; Polyethersulfones
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
  • H01M8/0204—Non-porous and characterised by the material
  • H01M8/0221—Organic resins; Organic polymers
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/02—Details
  • H01M8/0289—Means for holding the electrolyte
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
  • H01M8/1018—Polymeric electrolyte materials
  • H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
  • H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
• • 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

Definitions

• the invention relates to aromatic polyethersulfone block copolymers, processes for their preparation and their use in fuel cells or as membranes for water treatment.
• polyelectrolytes for solid polymeric fuel cells based on aromatic polyethersulfone block copolymers is known per se.
• Corresponding copolymers are described in EP-A-1 394 879. These are in particular polyethersulfone (PES) polyphenylsulfone (PPSU) block copolymers which have been sulfonated with concentrated sulfuric acid at room temperature.
• PES polyethersulfone
• PPSU polyphenylsulfone
• US 2004/0138387 relates to block copolymers and their use as polymer electrolyte in fuel cells.
• the sulfonation is carried out with concentrated sulfuric acid at temperatures of 40 to 60 0 C.
• the polymers are, in particular, polyether ether sulfones.
• EP-A-1 113 517 relates to polymer electrolytes and processes for their preparation.
• a block copolymer of dihydroxydiphenylsulfone, dihydroxybiphenyl and dichlorodiphenyl sulfone prepared and subsequently sulfonated with concentrated sulfuric acid.
• the object of the present invention is to provide improved aromatic polyethersulfone block copolymers which can be used as polyelectrolyte in the production of fuel cells or as membrane for water treatment.
• the polymers should show improved application properties or a suitable property profile, in particular with respect to the proton conductivity, methanol permeation and swelling. For water treatment, they should also show good chemical resistance and resistance to fouling.
• the object is achieved according to the invention by an aromatic polyethersulfone block copolymer comprising hydrophilic segments which have sulfonic acid groups and hydrophobic segments which have no sulfonic acid groups, the weight fraction of hydrophilic segments being 0.02 to 0.35, based on the total Block copolymer (corresponding to 2 to 35 wt .-%).
• the object is also achieved by a process for preparing such aromatic polyethersulfone block copolymers, wherein an aromatic polyethersulfone block copolymer is sulfonated with concentrated sulfuric acid at a temperature in the range of 20 to 70 0 C.
• the object is also achieved by the use of the above aromatic polyethersulfone block copolymers as polyelectrolyte len for the production of fuel cells or for the production of membranes for water treatment.
• the invention also relates to a fuel cell containing as polyelectrolyte an aromatic polyethersulfone block copolymer as described above.
• the invention further relates to a membrane for water treatment, comprising an aromatic polyethersulfone block copolymer, as described above.
• aromatic polyethersulfone block copolymers according to the invention have an advantageous spectrum of mechanical and chemical application properties which make them suitable both as polyelectrolyte and for the production of membranes.
• the hydrophilic segments are distinguished from the hydrophobic segments in that the hydrophilic segments have sulfonic acid groups but the hydrophobic segments do not.
• the proportion by weight of hydrophilic segments is in the range of 0.02 to 0.35, preferably 0.05 to 0.30.
• the proportion by weight is 0.15 to 0.35.
• Such block copolymers are particularly suitable as polyelectrolytes for the production of fuel cells.
• the proportion by weight is 0.02 to 0.25.
• the proportions by weight always refer to the entire block copolymer.
• Such block copolymers are particularly suitable for the production of membranes for water treatment.
• hydrophilic segments are understood as meaning those segments which have sulfonic acid groups. Accordingly, hydrophobic segments are understood as meaning those segments which have no sulfonic acid groups.
• the hydrophilic segments can consist of any aromatic hydrophilic segments, provided they have sulfonic acid groups and are suitable for the preparation of block copolymers with the hydrophobic segments.
• the hydrophilic segments preferably contain sulfonated polyphenylene sulfone (PPSU) building blocks. These preferably have the general formula (2)
• Ar is a bivalent aromatic radical and m is an integer from 3 to 1500, preferably 5 to 500.
• the radical Ar may have the meaning given in EP-A-1 394 879 for the structures of the general formula (2).
• the aromatic radical Ar is preferably a polynuclear aromatic radical, preferably a biphenyl radical of the general formula (3)
• This is particularly preferably a Polyphenylsulfonrest.
• the phenyl groups can also be linked via a group -C (CH 3 ) 2 -.
• the remainder of the general formula (2) is converted into the hydrophilic segments by subsequent sulfonation.
• each of the phenylene groups in the formula (3) has a sulfonic acid group after sulfonation.
• the sulfonic acid group is preferably in the ortho position to the bound oxygen.
• the hydrophobic segments are preferably polyethersulfone segments.
• the hydrophobic segments preferably have the general formula (1)
• n integer 3 to 1500.
• the polyethersulfone particularly preferably has the formula (4)
• a block copolymer in particular of polyethersulfone units and polyphenylsulfone units, is first prepared, and the resulting block copolymer is subsequently selectively sulfonated with concentrated aqueous sulfuric acid (about 98% strength).
• concentrated aqueous sulfuric acid about 98% strength
• the aromatic polyethersulfone block copolymers are preferably sulfonated with concentrated sulfuric acid at a temperature in the range of 20 to 70 ° C, preferably 25 to 50 ° C.
• the polyethersulfone blocks and polyphenylsulfone blocks are preferably present in the block copolymer according to the invention such that the polymer blocks exhibit a phase separation in the size range from 10 to 100 nm.
• the sulfonated block copolymers PES / sPPSU have the advantage of a strong separation in the range of 10 to 100 nm compared to random copolymers.
• the block copolymers simultaneously obtain properties such as mechanical stability, low surface swelling in water / methanol and high water permeability or high ionic conductivity.
• This combination of partly opposite properties is compatible with statistical copolyme- can not be realized.
• statistical PES-PPSU copolymers having PPSU contents of more than 20% can not or hardly be isolated after sulfonation due to the high swelling or the solubility in water.
• Block copolymers with PPSU contents of up to 35% by weight can still be isolated.
• M is preferably a number in the range of 5 to 500.
• the hydrophilic segments correspond to the formula (7) given in EP-A-1 394 879 and the hydrophobic segments correspond to the formula (8) given there.
• the sulfonic acid groups of the block copolymer according to the invention preferably have an ion exchange capacity of 0.07 to 1, 43 mmol / g, more preferably from 0.178 to 1, 07 mmol / g.
• the preparation of the aromatic polyethersulfone block copolymers according to the invention is carried out by first synthesizing a non-sulfonated block copolymer, which is subsequently sulfonated.
• the aromatic dihalide comprises bis (4-chlorophenyl) sulfone, bis (4-fluorophenyl) sulfone, bis (4-bromophenyl) sulfone, bis (4-iodophenyl) sulfone, bis (2-chlorophenyl) sulfone, bis (2-fluorophenyl) sulfone, bis (2-methyl-4-chlorophenyl) sulfone, bis (2-methyl-4-fluorophenyl) sulfone, bis (3,5-dimethyl-4-chlorophenyl) sulfone, and bis (3,5-dimethyl-4-fluorophenyl) sulfone.
• bis (4-chlorophenyl) sulfone and bis (4-fluorophenyl) sulfone are preferred.
• the dihydric alcohol includes bis (4-hydroxyphenyl) sulfone and bis (4-hydroxyphenyl) ketone, with bis (4-hydroxyphenyl) sulfone being preferred.
• the dialkali metal salt of a dihydric phenol is obtainable by the reaction between the dihydric phenol and the alkali metal compound such as potassium carbonate, potassium hydroxide, sodium carbonate or sodium hydroxide.
• the alkali metal compound such as potassium carbonate, potassium hydroxide, sodium carbonate or sodium hydroxide.
• a combination of sodium or potassium salt of bis (4-hydroxyphenyl) sulfone and bis (4-chlorophenyl) sulfone or bis (4-fluorophenyl) sulfone is a preferred combination of the dialkali metal salt of a dihydric phenol and the aromatic dihalide.
• the reaction between the dialkali metal salt of a dihydric phenol and the aromatic dihalide is carried out in a polar solvent such as dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylformamide. N, N-dimethylacetamide and di-phenylsulfone.
• a polar solvent such as dimethyl sulfoxide, sulfolane, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylformamide. N, N-dimethylacetamide and di-phenylsulfone.
• the reaction temperature is preferably 140 ° C. to 320 ° C.
• the reaction time is preferably 0.5 hour to 100 hours.
• the dihydric phenol or the aromatic dihalide are used in equimolar amounts, and either a monohydric phenol, for example, phenol, cresol, 4-phenylphenol or 3-phenylphenol, or an aromatic halide, for example, 4-chlorophenylphenylsulfone, 1-chloro 4-nitrobenzene, 1-chloro-2-nitrobenzene, 1-chloro-3-nitrobenzene, 4-fluorobenzophenone, 1-fluoro-4-nitrobenzene, 1-fluoro-2-nitrobenzene or 1-fluoro-3-nitrobenzene, added.
• a monohydric phenol for example, phenol, cresol, 4-phenylphenol or 3-phenylphenol
• an aromatic halide for example, 4-chlorophenylphenylsulfone, 1-chloro 4-nitrobenzene, 1-chloro-2-nitrobenzene, 1-chloro-3-nitrobenzene, 4-fluorobenzophenone, 1-fluoro-4-nitro
• the degree of polymerization of the prepolymer is in the range of from 3 to 1500, preferably from 5 to 500. At a degree of polymerization of less than 3, the block copolymer synthesized therefrom scarcely exhibits the desired properties. At a degree of polymerization of more than 1500, it is difficult to synthesize the block copolymer.
• a preferred hydrophobic segment prepolymer has a structure represented by the chemical formula (1):
• the non-sulfonated hydrophilic segment prepolymer used in the method (1) is preferably synthesized from an aromatic dihalide and a dihydric phenol, which phenol has no electron-withdrawing group on an aromatic ring.
• the divalent phenol having no electron donating group on its aromatic ring includes hydroquinone, resorcinol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, 2, 2'-biphenol, bis (4-hydroxyphenyl) ether, bis (2-hydroxyphenyl) ether, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl ) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) hexafluoropropane and 9 , 9-bis (4-hydroxyphenyl) fluorene.
• hydroquinone 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, 2,2'-biphenol, bis (4-hydroxyphenyl) ether, bis (2-hydroxyphenyl) ether and 9,9-bis (4-hydroxyphenyl) fluorene.
• the aromatic dihalide includes those having a sulfone group, which are useful for the synthesis of the prepolymer of a hydrophobic segment, and further, those having a ketone group, such as 4,4'-difluorobenzophenone and 2,4'-difluorobenzophenone.
• the most desirable prepolymer of a non-sulfonated hydrophilic segment is one having the structure of the chemical formula (2):
• Ar represents a divalent aromatic radical group; and
• m represents an integer of 3 to 1,500.
• Polyether for example, under the name of Sumikaexcel ® sumi- tomo Chemical Co., Ltd. available.
• Polyarylether are available for example under the name Radel ® from Solvay.
• Modification of the molecular weight and end groups of commercially available polymers can be effected by ether exchange with the above-mentioned alkali metal salts of the dihydric phenols or the monohydric phenol under the same conditions as for the synthesis of the aromatic polyethersulfones described in RN Johnson et al. J. Polym. Sei., AI 1 VoI. 5, 2375 (1967) or JP-B-46-21458.
• the non-sulfonated block copolymer is synthesized by the reaction between the above-described hydrophobic segment prepolymer and the prepolymer of a non-sulfonated hydrophilic segment.
• the prepolymer of a hydrophobic segment has a halogen end group or an end group of an alkali metal salt of a phenol. It is preferable that the prepolymer of a non-sulfonated hydrophilic segment has a corresponding halogen end group or a corresponding terminal group of an alkali metal salt of a phenol.
• the reaction is carried out in the aforementioned solvent at a reaction temperature of 140 0 C to 320 0 C for a reaction time of 0.5 hours to 100 hours. This reaction is described, for example, in Z. Wu et al., Angew. Makromol. Chem., Vol. 173, 163 (1989) and Z. Wang et al., Polym. Int., Vol. 50, 249 (2001).
• the non-sulfonated block copolymer can also be synthesized by the reaction between the two segment prepolymers both having an end group of an alkali metal salt of a phenol by using a linking agent in the same manner.
• the above-mentioned aromatic dihalides can be used as the linking agent.
• Aromatic difluorides such as bis (2-fluorophenyl) sulfone and bis (4-fluorophenyl) sulfone are preferred as the compound because of their high reactivity. Sulfonation of products from direct coupling is possible.
• the sulfonation is carried out according to the invention at a temperature of 20 to 70 0 C with sulfuric acid.
• the sulfuric acid is preferably 90 to 98% by weight, in particular 98% by weight. In this temperature range, only the hydrophilic segment is successfully sulfonated because the hydrophobic segment, which has an electron-withdrawing group attached to the aromatic ring, is not sulfonated.
• the degree of sulfonation is thus determined by the polyphenylsulfone (PPSU) segments which are incorporated in the polycondensation. During the sulfonation all PPSU blocks are sulfonated. The control of the degree of sulfonation is very easily adjustable via the molecular weight and the segment length of the PES / PPSU block copolymers.
• PPSU polyphenylsulfone
• the sulfonated block copolymers of the invention have the advantage of a strong phase separation compared to random copolymers.
• the polymer blocks preferably show a phase separation in the size range of 10 to 100 nm.
• Polymers of the invention have, based on the unsulfonated polymer, preferably a weight average molecular weight (Mw) in the range of 1 to 200 kg / mol, more preferably 5 to 100 kg / mol, particularly preferably 5 to 70 kg / mol, determined by gel permeation chromatography / Size Exclusion Chromatography (GPC / SEC). The method is well known to the skilled person and corresponds to the state of the art.
• the invention also relates to the use of the aromatic polyethersulfone block copolymers, as described above, as a polyelectrolyte for the production of fuel cells or for the production of membranes for water treatment.
• the use of polyelectrolyte membranes in fuel cells is generally known. Reference may be made, for example, to EP-A-1 394 879, EP-A-1 113 517, US 2004/0138387, EP-A-1 669 391 and EP-A-1 855 339.
• Polyelectrolyte membranes can be obtained, for example, by film formation methods using the block copolymers of the present invention.
• the film-forming method for obtaining a polyelectrolyte membrane for a solid polymer fuel cell of the present invention starting from a block copolymer of aromatic polyethersulfone thus prepared is not particularly limited.
• the block copolymer is dissolved from an aromatic polyethersulfone in a polar solvent such as dimethylsulfoxide, sulfolane, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylformamide, N, N-dimethylacetamide or diphenylsulfone, the solution poured onto a support, and the (polar) solvent is, for. B. removed by evaporation.
• a polar solvent such as dimethylsulfoxide, sulfolane, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N, N-dimethylformamide, N, N-dimethylacetamide or diphenyl
• the film thickness is 5 to 200 ⁇ m, preferably 10 to 150 ⁇ m.
• a film thinner than 5 ⁇ m is typically difficult to handle.
• a film thicker than 200 ⁇ m is unfavorable since a fuel cell which has a contains such membrane, having a reduced efficiency in power generation.
• the polyelectrolyte membrane of the present invention may be in the form of a metal salt with respect to a part of its sulfonic acid groups as far as the properties of the present invention are not deteriorated.
• the membrane may be reinforced by fibers, a porous film and the like.
• the polyelectrolyte membrane may contain inorganic acids mixed therewith, for example, phosphoric acid, hypophosphorous acid and sulfuric acid, or salts thereof, perfluoroalkylsulfonic acids having 1 to 14 carbon atoms or salts thereof, perfluoroalkylcarboxylic acids having 1 to 14 carbon atoms or salts the same, inorganic substances, for example, platinum, silica gel, silica and zeolites and other polymers.
• inorganic acids for example, phosphoric acid, hypophosphorous acid and sulfuric acid, or salts thereof, perfluoroalkylsulfonic acids having 1 to 14 carbon atoms or salts thereof, perfluoroalkylcarboxylic acids having 1 to 14 carbon atoms or salts the same, inorganic substances, for example, platinum, silica gel, silica and zeolites and other polymers.
• the production of the fuel cell per se is not limited.
• MEU membrane-electrode assembly
• GDE gas diffusion electrode
• CCM catalyst coated membrane
• the aromatic polyethersulfone block copolymers according to the invention can also be used for the production of membranes for water treatment.
• the preparation of such membranes is for example in Angew. Chem. Int. Ed. 2008, 47, pages 1 to 7 described.
• the membrane is produced by casting a solution of the polymer on a level surface such as a glass plate and then removing the solvent. The removal of the solvent can be carried out for example by heating or by applying a negative pressure.
• Membranes for water treatment are generally semipermeable membranes which allow separation of dissolved and suspended particles of water, the separation process itself being either pressure or electrically driven.
• Typical, but not limiting, membrane application examples for the polymers according to the invention are pressure-driven membrane technologies such as micro filtration (MF, separation limit about 0.08 to 2 ⁇ m, very small, suspended particles, colloids, bacteria), ultrafiltration (UF, separation limit about 0.005 up to 0.2 ⁇ m, organic particles> 1000 MW, viruses, bacteria, colloids), nanofiltration (NF, separation limit 0.001 to 0.01 ⁇ m, organic particles> 300 MW, THM precursors, viruses, bacteria, colloids, dissolved substances) or Reverse osmosis (RO, separation limit 0.0001 to 0.001 ⁇ m, ions, organic substances> 100 MW).
• MF micro filtration
• UF ultrafiltration
• NF separation limit 0.001 to 0.01 ⁇ m
• RO Reverse osmosis
• the invention also relates to corresponding fuel cells, comprising as polyelectrolyte an aromatic polyethersulfone block copolymer according to the invention, and a membrane for water treatment, containing as membrane material an aromatic polyethersulfone block copolymer according to the invention.

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• 2010
  • 2010-06-15 CN CN2010800265661A patent/CN102803341A/zh active Pending
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