US20100063168A1 - Ionomers with ionogenic groups in the sidechain - Google Patents
Ionomers with ionogenic groups in the sidechain Download PDFInfo
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- US20100063168A1 US20100063168A1 US11/573,982 US57398205A US2010063168A1 US 20100063168 A1 US20100063168 A1 US 20100063168A1 US 57398205 A US57398205 A US 57398205A US 2010063168 A1 US2010063168 A1 US 2010063168A1
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- 0 *[C-]([2*])C([2*])=O.CC.CC.CC.CC=[N-].COC=[N-].C[O-].C[S-].[2*]C([2*])=C([2*])[O-].[H][C-](C)C Chemical compound *[C-]([2*])C([2*])=O.CC.CC.CC.CC=[N-].COC=[N-].C[O-].C[S-].[2*]C([2*])=C([2*])[O-].[H][C-](C)C 0.000 description 5
- UILUEWRQGYRTLP-UHFFFAOYSA-N BrCCCCBr.CCCC(Br)C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(C(Br)CCC)C=C(C)C=C1.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 Chemical compound BrCCCCBr.CCCC(Br)C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(C(Br)CCC)C=C(C)C=C1.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 UILUEWRQGYRTLP-UHFFFAOYSA-N 0.000 description 1
- LBNPVAOFDFFLGW-UHFFFAOYSA-N BrCCCCCCBr.CCCCCC(Br)C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(C(Br)CCCCC)C=C(C)C=C1.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 Chemical compound BrCCCCCCBr.CCCCCC(Br)C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(C(Br)CCCCC)C=C(C)C=C1.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 LBNPVAOFDFFLGW-UHFFFAOYSA-N 0.000 description 1
- JKZWBUYEQCVFKI-UHFFFAOYSA-N BrCCCCCCCCCCCCBr.CCCCCCCCCCCC(Br)C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(C(Br)CCCCCCCCCCC)C=C(C)C=C1.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 Chemical compound BrCCCCCCCCCCCCBr.CCCCCCCCCCCC(Br)C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(C(Br)CCCCCCCCCCC)C=C(C)C=C1.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 JKZWBUYEQCVFKI-UHFFFAOYSA-N 0.000 description 1
- PYRCKJQVECHOSJ-UHFFFAOYSA-N C.CCOP(=O)(CCBr)OCC.CCOP(=O)(CCC1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(CCP(=O)(CC)CC)C=C(C)C=C1)OCC.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 Chemical compound C.CCOP(=O)(CCBr)OCC.CCOP(=O)(CCC1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(CCP(=O)(CC)CC)C=C(C)C=C1)OCC.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 PYRCKJQVECHOSJ-UHFFFAOYSA-N 0.000 description 1
- SCUFVONAYKUZJX-UHFFFAOYSA-N CCCC(Br)C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(C(Br)CCC)C=C(C)C=C1.ICCCCI.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 Chemical compound CCCC(Br)C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C(C(Br)CCC)C=C(C)C=C1.ICCCCI.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 SCUFVONAYKUZJX-UHFFFAOYSA-N 0.000 description 1
- NYAQHWTZLOCGLV-UHFFFAOYSA-N COC1=CC=C(C(C)(C)C2=CC=C(OC3=CC=C(S(=O)(=O)C4=C(CP(=O)(Cl)Cl)C=C(C)C=C4)C(CP(=O)(Cl)Cl)=C3)C=C2)C=C1.O=P(Cl)(Cl)CCl.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 Chemical compound COC1=CC=C(C(C)(C)C2=CC=C(OC3=CC=C(S(=O)(=O)C4=C(CP(=O)(Cl)Cl)C=C(C)C=C4)C(CP(=O)(Cl)Cl)=C3)C=C2)C=C1.O=P(Cl)(Cl)CCl.[Li]C1=CC(OC2=CC=C(C(C)(C)C3=CC=C(OC)C=C3)C=C2)=CC=C1S(=O)(=O)C1=C([Li])C=C(C)C=C1 NYAQHWTZLOCGLV-UHFFFAOYSA-N 0.000 description 1
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- B01D71/68—Polysulfones; Polyethersulfones
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Definitions
- Ionomer membranes containing phosphoric acid or phosphonic acid have received in recent years a growing interest because the phosphoric and phosphonic acid groups show water-free proton conductivity, in that phosphoric acid groups or phosphonic acid groups can act as proton donator as well as as proton acceptor.
- This water-free proton conductivity of phosphoric acids is especially interesting for fuel cells in the temperature range between 100° C. and 200° C., because in this temperature range in fuel cells the vapour pressure of water is very low so that sulfonic acid containing ionomer membranes do not work anymore, because they need water molecules as proton acceptors. From the literature several membrane types are known, whose proton conductivity is generated from phosphoric acid or phosphonic acids.
- the aim of the invention is to provide ionomers and ionomer membranes with the ionic group on a flexible side chain which has a positive impact on the proton conductivity of the ionomers.
- the aim is furthermore to provide processes for the production of these polymeric proton conductors.
- FIG. 1 Ionomers according to the invention are shown in FIG. 1 .
- the method 1 is depicted in FIG. 2 .
- the method 2 is depicted in FIG. 3 .
- the side chain halogenated polymers can be converted via Michaelis-Arbusov reaction or related reactions and subsequent hydrolysis towards polymers with the phosphonic acid group in the side chain. This reaction is depicted in FIG. 4 .
- main chains all kinds of polymers are possible. Preferred as main chains are however:
- (Het)aryl main chain polymers like:
- Suitable reagents for the deprotonation of the aryl polymer are n-butyllithium, sec-butyllithium, tert. butyllithium, methyllithium, phenyllithium, Grignard compounds like phenylmagnesiumhalide and other Grignard compounds, lithium diisopropylamide, and other lithium amides, sodium naphtalide, potassium naphtalide, zinc organic compounds (“Rieke metals”)
- Suitable solvents for the metal organic reaction are ether solvents like THF, diethylether, glyme, diglyme, triglyme, dioxane and other ether solvents as well as hydrocarbon solvents C n H 2n+2 , cyclohexane, benzene, toluene, xylole and other C—H— aromatic solvants and any other mixtures thereof and with ether solvents.
- the compounds with nucleophilically substitutable halogens and ionogenic groups may contain as halogene F, Cl, Br, or I. Preferred are Cl, Br and I. Also mixtures of organic compounds with different halgenes and different alkyl chain lengths can be used.
- the dihalogen alcanes according to the invention method 2 can be also mixed dihalogen alcanes, that is compounds like Br—(C(R 1 ) 2 ) x —I, where both halogen atoms have different reactivity to assure that no cross-linking takes place during method 2 . If for example the compound I—(CH 2 )—Cl is reacted with lithiated PSU, I is preferred to be exchanged nucleophilically. Thereby Cl, Br and I are preferred.
- mixtures of dihalogene compounds with different halgenes and different alkyl chain lengths can be used. Also compounds like Hal-(C(R 1 ) 2 ) x -Aryl-Hal are possible. According to the invention also Hal-(C(R 1 ) 2 ) x —Z-Aryl-Hal are possible.
- halogenated hetaromates can be used. Some of these hetaromates are shown in FIG. 6 .
- the hetaromates may contain in addition organic rests which do not react with the reactands of the process according to the invention.
- Suitable nucleophilic groups for the reaction with the side chain halogenated polymers are shown in FIG. 7 .
- sulfinate groups SO 2 M are especially preferred.
- the sulfinates react with the halogenes preferred by S-Alkylation, as depicted in FIG. 8 for the reaction of a side-chain halogenated polymer with lithium sulfinatophenylphosphonic acid dialkylester.
- membranes with a proton conducting functional group at the end of an alkyl-, aryl- or alkylaryl side chain can be made according to the following process:
- Suitable solvents for the reaction of the side-chain halogenated polymers with compounds containing a nucleophilic group and the ionic group or their non-ionic precursor are ether solvents as described above, hydrocarbon solvents (aliphatic or aromatic, as described above), dipolar-aprotic solvents such as NMP, DMAc, DMF, DMSO, Sulfolan, protic solvents such as alcoholes C n H 2n+1 , water or any other mixtures of these solvents with each other.
- the reaction temperature for the metal organic reaction is from ⁇ 100° C. to +100° C. Preferred is the temperature range from ⁇ 80 to 0° C.
- the reaction temperature for the reaction of the deprotonated polymer with the organic compound containing a halogen atom and one or more ionic groups or their non-ionic precursors is from ⁇ 100° C. to +100° C. Preferred is the temperature range from ⁇ 80 to 0° C.
- the reaction temperature for the reaction of the deprotonated polymer with the dihalogen compounds is from ⁇ 100° C. to +100° C. Preferred is the temperature range from ⁇ 80 to 0° C.
- the reaction temperature for the reaction of the side-chain halogenated polymer with nucleophilic groups and ionic groups or their non-ionic precursors is from ⁇ 100° C. to +200° C. Preferred is the temperature range from ⁇ 80 to +150° C.
- Suitable solvents for the Michaelis-Arbusov-reaction of the side-chain halogenated polymers are ether solvents as described above, hydrocarbon solvents (aliphatic or aromatic, as described above), dipolar-aprotic solvents such as NMP, DMAc, DMF, DMSO, Sulfolan, protic solvents such as alcoholes C n H 2n+1 , water or any other mixture of these solvents with each other.
- dipolar-aprotic solvents especially preferred is DMSO.
- Suitable catalyst systems for the Michaelis-Arbusov-reaction are NiCl 2 (with use of Triethylphosphite as phosphonation agent) or Pd(PPh 3 ) 4 /triethylamine (with use of (EtO) 2 POH as phosphonation agent). Preferred is Pd(PPh 3 ) 4 /triethylamine as catalyst system.
- reaction temperature for the Michaelis-Arbusov-reaction of the side-chain halogenated polymer with nucleophilic groups and ionic groups or their non-ionic precursors is from ⁇ 100° C. to +200° C. Preferred is the temperature range from 0 to +150° C.
- Suitable conditions for hydrolysis of the proton-conducting groups are:
- the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on.
- the precipitated polymer is dried at 60° C. From the product, the following analyses are prepared: 1 H—, 13 C and 31 P-NMR, elemental analysis.
- the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of Chlormethanphosphonklaichloride (2-fold excess) is added into the reaction mixture as fast as possible.
- the solution changes colour at once to black and in a few minutes back to yellow-orange.
- the reaction mixture is stirred for 6 h at ⁇ 40° C., increases the temperature for 24 h to ⁇ 20° C., then for 12 h to 0° C.
- the polymer is precipitated from the solution with 4 l demineralised water. The polymer soon forms a yellow cake in the upper THF layer, which is separated and digested with methanol for 12 h.
- the thus purified polymer is dried at 60° C. From the product, the following analyses are prepared: 1 H—, 13 C and 31 P-NMR, elemental analysis.
- the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibromhexane is added into the reaction mixture as fast as possible.
- reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
- the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
- the thus purified polymer is dried at 25° C. under vacuum.
- the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibrombutane is added into the reaction mixture as fast as possible.
- reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
- the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
- the thus purified polymer is dried at 25° C. under vacuum.
- the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of dibromdodecane is added into the reaction mixture as fast as possible.
- reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
- the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
- the thus purified polymer is dried at 25° C. under vacuum.
- the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of diiodbutane is added into the reaction mixture as fast as possible.
- reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
- the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
- the thus purified polymer is dried at 25° C. under vacuum.
- the reaction flask is loaded with THF under inert gas. Subsequently, the dried polymer powder is added under stirring and vigorous flushing with Argon. After the polymer is dissolved, it is cooled down to ⁇ 60° C., under vigorous flushing with Argon. Then the polymer solution is titrated with n-BuLi (14 ml 2.5N n-BuLi, drum), until a slight yellow/orange colour indicates that the polymer solution is water-free from now on. Then within 10 min the 10N n-BuLi is syringed in. The stirring is continued for 2 hours. Then the solution of diioddecane is added into the reaction mixture as fast as possible.
- reaction mixture is stirred for 12 h at ⁇ 20° C., the temperature is increased to 0° C. for 4 h.
- the solution is hydrolysed with 10 ml MeOH, precipitated in 2 l MeOH, digested in MeOH and washed on the filter twice.
- the thus purified polymer is dried at 25° C. under vacuum.
- the solvent is evaporated in a ventilated or vacuum drying ovenat increased temperature of 50 to 140° C.
- a ventilated or vacuum drying ovenat increased temperature of 50 to 140° C.
- the sulfinate-S-alkylation of the sulfinato-benzolphosphonic acid ester and the diiodbutane takes place and the membrane cross-links.
- the membrane is posttreated to saponificate the phosphonic acid ester with 48% HBr or concentrated HCl under reflux.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US13/330,614 US8742021B2 (en) | 2004-08-20 | 2011-12-19 | Ionomers with ionic groups in the side chain |
US14/293,904 US9403162B2 (en) | 2004-08-20 | 2014-11-12 | Ionomers with ionic groups in the side chain |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE102004041336 | 2004-08-20 | ||
DE102004041336.3 | 2004-08-20 | ||
PCT/DE2005/001504 WO2006018020A2 (de) | 2004-08-20 | 2005-08-20 | Ionomere mit ionogenen gruppen in der seitenkette |
Related Parent Applications (1)
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PCT/DE2005/001504 A-371-Of-International WO2006018020A2 (de) | 2004-08-20 | 2005-08-20 | Ionomere mit ionogenen gruppen in der seitenkette |
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US13/330,614 Continuation US8742021B2 (en) | 2004-08-20 | 2011-12-19 | Ionomers with ionic groups in the side chain |
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US11/573,982 Abandoned US20100063168A1 (en) | 2004-08-20 | 2005-08-20 | Ionomers with ionogenic groups in the sidechain |
US13/330,614 Expired - Fee Related US8742021B2 (en) | 2004-08-20 | 2011-12-19 | Ionomers with ionic groups in the side chain |
US14/293,904 Expired - Fee Related US9403162B2 (en) | 2004-08-20 | 2014-11-12 | Ionomers with ionic groups in the side chain |
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US13/330,614 Expired - Fee Related US8742021B2 (en) | 2004-08-20 | 2011-12-19 | Ionomers with ionic groups in the side chain |
US14/293,904 Expired - Fee Related US9403162B2 (en) | 2004-08-20 | 2014-11-12 | Ionomers with ionic groups in the side chain |
Country Status (5)
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US (3) | US20100063168A1 (ja) |
EP (1) | EP1786544A2 (ja) |
JP (3) | JP2008510845A (ja) |
DE (1) | DE112005002051A5 (ja) |
WO (1) | WO2006018020A2 (ja) |
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EP1987081B1 (de) * | 2006-02-16 | 2012-09-12 | Basf Se | Oligo- und polymere aromatische phosphonsäuren, deren blends, verfahren zu deren herstellung und anwendungen als polyelektrolyte |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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US6723757B1 (en) * | 1998-04-18 | 2004-04-20 | Universitat Stuttgart Lehrstuhl | Engineering ionomeric blends and engineering ionomeric blend membranes |
US7288599B2 (en) * | 2002-02-28 | 2007-10-30 | Jochen Kerres | Oligomers and polymers containing sulfinate groups, and method for producing the same |
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US4598137A (en) * | 1984-11-30 | 1986-07-01 | Canadian Patents And Development Limited | Polyarylene polyethersulfone ionomers |
JPH08283413A (ja) * | 1995-04-12 | 1996-10-29 | Dainippon Ink & Chem Inc | ポリフェニレンスルフィド共重合体アイオノマーの製法 |
KR19990028586A (ko) * | 1995-06-30 | 1999-04-15 | 악커만,야코비 | 중합체 결합 포스포늄 염을 갖는 폴리아릴렌 설파이드 및 이의제조방법 |
JP3561250B2 (ja) * | 2001-09-21 | 2004-09-02 | 株式会社日立製作所 | 燃料電池 |
WO2003060011A2 (de) * | 2001-11-22 | 2003-07-24 | HÄRING, Rima | Modifizierte kovalent vernetzte polymere |
-
2005
- 2005-08-20 US US11/573,982 patent/US20100063168A1/en not_active Abandoned
- 2005-08-20 WO PCT/DE2005/001504 patent/WO2006018020A2/de active Application Filing
- 2005-08-20 JP JP2007526201A patent/JP2008510845A/ja active Pending
- 2005-08-20 DE DE112005002051T patent/DE112005002051A5/de not_active Withdrawn
- 2005-08-20 EP EP05778891A patent/EP1786544A2/de not_active Withdrawn
-
2011
- 2011-12-19 US US13/330,614 patent/US8742021B2/en not_active Expired - Fee Related
-
2012
- 2012-06-14 JP JP2012135259A patent/JP5766655B2/ja not_active Expired - Fee Related
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2014
- 2014-04-22 JP JP2014088619A patent/JP2014221896A/ja active Pending
- 2014-11-12 US US14/293,904 patent/US9403162B2/en not_active Expired - Fee Related
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6723757B1 (en) * | 1998-04-18 | 2004-04-20 | Universitat Stuttgart Lehrstuhl | Engineering ionomeric blends and engineering ionomeric blend membranes |
US7288599B2 (en) * | 2002-02-28 | 2007-10-30 | Jochen Kerres | Oligomers and polymers containing sulfinate groups, and method for producing the same |
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Publication number | Publication date |
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JP5766655B2 (ja) | 2015-08-19 |
JP2008510845A (ja) | 2008-04-10 |
US20120245237A1 (en) | 2012-09-27 |
US9403162B2 (en) | 2016-08-02 |
JP2014221896A (ja) | 2014-11-27 |
WO2006018020A2 (de) | 2006-02-23 |
US20150064609A1 (en) | 2015-03-05 |
US8742021B2 (en) | 2014-06-03 |
JP2012224856A (ja) | 2012-11-15 |
WO2006018020A3 (de) | 2006-05-18 |
DE112005002051A5 (de) | 2008-08-28 |
EP1786544A2 (de) | 2007-05-23 |
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