[go: up one dir, main page]

WO1997011099A9 - Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises - Google Patents

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

Info

Publication number
WO1997011099A9
WO1997011099A9 PCT/DE1996/001599 DE9601599W WO9711099A9 WO 1997011099 A9 WO1997011099 A9 WO 1997011099A9 DE 9601599 W DE9601599 W DE 9601599W WO 9711099 A9 WO9711099 A9 WO 9711099A9
Authority
WO
WIPO (PCT)
Prior art keywords
phenylene
copoly
polymer
solid electrolyte
polymeric solid
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.)
Ceased
Application number
PCT/DE1996/001599
Other languages
German (de)
English (en)
Other versions
WO1997011099A3 (fr
WO1997011099A2 (fr
Filing date
Publication date
Priority claimed from DE19535086A external-priority patent/DE19535086B4/de
Application filed filed Critical
Priority to EP96943846A priority Critical patent/EP0852071A2/fr
Priority to JP9512297A priority patent/JPH11515040A/ja
Publication of WO1997011099A2 publication Critical patent/WO1997011099A2/fr
Publication of WO1997011099A9 publication Critical patent/WO1997011099A9/fr
Publication of WO1997011099A3 publication Critical patent/WO1997011099A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Definitions

  • the invention relates to a polymer Fest ⁇ body electrolyte with a hydrophobic backbone, which is at least partially functionalized by ionic groups.
  • Polymeric solid electrolytes are ion-exchanging membranes consisting of polymers with ionic groups. They have high ionic conductivity and, in contrast to liquid systems, mechanical stability. They come in ver ⁇ different applications, such. As ion exchangers, (water) electrolyzers, batteries or Brennstoffzel ⁇ len used.
  • the invention relates to polymer electrolyte, which are mainly used 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 available only with well-defined parameters (thickness, ion exchange capacity) and are not thermoplastic or processable from solutions. Furthermore, the high production costs negatively 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) are disclosed in US 3,259,592, US 3,484,293 or US 3,528,858. Moreover, membrane materials are based on aromatic Polyether ketones known from EP 0 575 807 A1 or EP 0 574 791 A2. Polymer electrolytes based on sulfonated poly (p-phenylene) s are described in WO 94/24717.
  • the sulfonated poly (p-phenylene) backbone polymers described by WO 94/24717 due to their rigid structure and high degree of crystallinity, must have solubilizing side chains to be processed.
  • the properties of the polymeric 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 ionically dissociable functional groups.
  • the charges generated in the presence of water and the hydrophobic backbone result in phase separation into ion-rich and ion-depleted regions.
  • the aggregated ions act as physical crosslinking sites for the polymer molecules. To this The result is a macroscopically elastic, thermally reversible, physical network.
  • US 3,376,235 describes a linear, sulfonated poly (p-phenylene) having 1 to 2 sulfonic acid groups per 10 phenylene rings.
  • Unsubstituted poly (p-phenylene) (PPP) is due to the rigid structure ("rigid rod") acid ⁇ crystalline, infusible and extremely insoluble. It is chemically and thermally very stable, but due to the properties mentioned hardly processable.
  • the sulfonation according to US Pat. No. 3,376,235 consequently requires very drastic conditions (oleum, reaction time of 1 to 50 hours at 25 to 200 ° C.). The products obtained are dark brown, still insoluble sulfonated materials. Due to the insolubility, however, no membranes can be produced from it.
  • the materials should 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 further developed should be suitable in particular for use as an electrolyte membrane in electrolysis devices or in fuel cells.
  • a polymeric solid electrolyte having a preferably hydrophobic backbone, which is at least partially functionalized by ionic groups, is further developed such that the backbone of the polymer has a copoly (m-phenylene) containing at least 20 mol% m-phenylene Contains units and of the following structure is:
  • R 1 to R 8 are hydrogen, aryl, oxyaryl, thioaryl,
  • the invention is based on the surprising finding that incorporation of m-phenylene units in PPP gives a soluble and meltable poly (m-phenylene-co-p-phenylene) despite the absence of solubilizing side chains.
  • the substitution with side chains for the processability is not absolutely necessary. Even without ring substitution, in the case of copolymers with predominantly m-linking of the repeat units, sulfonation and electrolyte preparation are possible.
  • the invention allows for the first time the synthesis of polymer electrolytes whose polymer molecules have only the ionic groups. The advantage of such systems over systems having longer side groups has already been found in WO 94/03503 for fluorinated materials.
  • the polymeric solid electrolytes of this invention are copoly (m-phenylene) s of structure (1) having at least 20 mole percent m-phenylene units.
  • a degree of functionalization with ionically dissociable groups greater than 0 and less than 1 is to be selected. This degree of functionalization is intended to mean the average number of ionic groups per repeat unit. In this case, the ionic groups can be randomly distributed over the polymer or preferably bound to specific repeat units.
  • the copoly (m-phenylene) s may be random, alternating, segmented or of a different order.
  • statistically structured copoly (m-phenylene) s are suitable for use as polymer electrolytes. Furthermore, a method is described below which makes it possible for the first time to synthesize such structured colpoly (m-phenylene) s in a statistical arrangement.
  • the substituents R 1 to R 8 may be hydrogen, aryl, oxyaryl, thioaryl, sulfonaryl, carbonylaryl, Oxyaryloxyaryl, hydroxyl or ionically dissociable groups.
  • Preferred ionically dissociable groups are, in particular, sulfonyl (-SO 3 H), carboxyl (-COH) or phosphoryl (-PO (OH) 2).
  • the substituent pairs R2 / R3 or R3 / R4 and / or R5 / R6 or R7 / R8 may also be fused arylene rings.
  • the polymer electrolytes of the present invention generally have a copoly (m-phenylene) backbone with similar hydrophobicity, such as the poly (tetrafluoroethylene) backbone of Nafion.
  • the polymeric solid-state electrolytes according to the invention have a thermally and chemically extremely resistant, highly hydrophobic backbone of copoly (m-phenylene) s, which is functionalized by ionic groups. In addition to a high proton conductivity, they show a very favorable swelling behavior, which manifests itself in good mechanical stability even at about 100 ° C. In addition, the materials of solutions in dipolar aprotic solvents can be processed and therefore accessible in any layer thicknesses. The abundance of In addition, the well-known phenyl coupling reactions known to the literature, which are well-known in the literature, could make the copoly (m-phenylene) s more accessible from inexpensive starting materials.
  • the invention also includes a method of preparing membranes of functionalized copoly (m-phenylene) s.
  • copoly (m-phenylene) s can in principle be done in two ways.
  • a copoly (m-phenylene) without ionic groups can be provided with such groups. This is preferably done by sulfonation.
  • the ionic groups can already be contained in the monomers during the polymerization.
  • the synthesis of copoly (m-phenylene) s can be carried out 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.
  • the feed-through takes place, for example, in a vigorously stirred two-phase mixture of approximately equal volumes of an aromatic in the boiling range of about 80 to 130 ° C. (for example toluene or benzene) and the aqueous solution of a base (for example 1 to 2) molar sodium carbonate solution).
  • the catalyst used is preferably tetrakis (triphenylphosphinepalladium-O) in concentrations of 0.1 to 0.6 mol%, but in particular in concentrations of 0.2 to 0.5 mol%, based on the boronic acid groups.
  • the reaction is carried out in boiling mixture between 1 and 12 hours.
  • the unsubstituted copoly (m-phenylene) s precipitate due to their insolubility during the reaction.
  • the formation of copolymers was demonstrated spectroscopically (IR and ⁇ 3 C solid-state NMR) and DSC.
  • Coply (m-phenylene) which is synthesized from 65% 3-Bromophenylboronklare and 35% 4- Bromphenylboronklare. It is surprisingly soluble in nonpolar solvents such as paraffins at about 180 ° C and has a melting point of 210 ° C. In this way, for the first time, an unsubstituted, fusible and soluble polyphenylene can be obtained.
  • ionically dissociable groups are not already present in the monomers, they may 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 which are suitable for the respective copoly (m-phenylene) can be determined by test series with progressively harder conditions.
  • a process for producing a polymeric solid electrolyte is specified such that the polymer is a copoly (m-phenylene) having the above ge called structure (I), which is sulfonated with the addition of a sulfonating agent.
  • the sulfonated copoly (m-phenylene) is dissolved in an organic solvent.
  • the solution is applied to a support on which the solvent is evaporated off. With the addition of water, the film remaining on the support is then peeled off and swelled.
  • the copoly (m-phenylene) s of the abovementioned structure can preferably be sulfonated very rapidly with the aid of chlorosulfonic acid in chloroform.
  • the ethanol present in chloroform as a stabilizer is first with an excess of Chlorosulfonic reacted and distilled the chloroform abde ⁇ .
  • the chloroform obtained in the distillation which fumes in the air 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. There are reaction times in the range of seconds.
  • aromatic rings of the polymer backbone (Ar) are sulfonated by chlorosulfonic acid (Equation (1).
  • the aromatic sulfonic acid is the compound Ar-S0 2 Cl, which is considered to be aryl-substituted chlorosulfonic acid leaves, in equilibrium (equation (2)).
  • the aryl-substituted chlorosulfonic acid should itself be capable of sulfonating again and of reacting with another aromatic ring to form an S0 2 bridge (equation (3)).
  • FIG. 3 l 3 C solid-state NMR spectra of copoly (m-phenylene-co-p-phenylene) s.
  • FIG. 1 shows the FT-IR spectra of the non-sulfonated copoly (m-phenylene) s (see FIG. 1 a), which can be prepared by means of the measure lb described below.
  • Fig. Lb shows the sulfonated with the measure 2 Copoly (m-phenylene) s and Figure lc over night with pure chlorosulfonic extremely strongly sulfonated copoly (m-phenylene) s, depending on the wavenumber in the range of 2000 cm-1 to 600 cm-1 (KBr-compacts).
  • the spectrum demonstrates the sulfonation of the copoly (m-phenylene) s according to equation (1).
  • the spectrum see FIG. 1c of the strongly sulfonated sample, one can see two strong bands at 1302.4 er 1 and 1167.8 cm -1 . They correspond to the symmetric and the asymmetric vibration of the crosslinking S0 2 groups, which have arisen according to equation (3).
  • the degree of sulfonation can be calculated from elemental analyzes (C, H, S determination).
  • the electrolyte membrane is produced according to the invention by dissolving the copoly (m-phenylene) s functionalized by ionic groups in an organic solvent, preferably a dipolar aprotic solvent, applying to a glass substrate and slowly evaporating the solvent. The resulting film is subsequently peeled off in water from the base, wherein a swollen membrane is formed.
  • an organic solvent preferably a dipolar aprotic solvent
  • Solid electrolyte membrane are preferably to take the following measures:
  • the solution is stirred for about 8 hours and treated with 200 ml of 1 N hydrochloric acid. This is cleared with vigorous stirring the initially cloudy organic phase and there is a viscous aqueous and a supernatant clear organic phase. Thereafter, the organic phase can be easily decanted. By rinsing with ether and decanting, residues of the product are to be removed from the flask.
  • the combined organic phases are extracted with a total of 500 ml of 2N sodium hydroxide in portions of 200, 100, 100, 100 ml.
  • the boronic acid passes as boronate into the sodium hydroxide solution.
  • the sodium hydroxide solution is again to be washed with 150 ml of diethyl ether. Then cool the solution to 0 ° C, adding 6N hydrochloric acid to a pH of 2 with further cooling.
  • the boronic acid precipitates in crystalline form and can be sucked off after standing. After drying in vacuo, 20 g (78% of theory) of crude product.
  • the boronic acids are to be purified by recrystallization. For this they are dissolved in as little as possible diethyl ether and precipitated by addition of pentane and cooling to -78 ° C. After drying in vacuo, 14.5 g (57%) of pure 3-bromophenylboronic acid or 15 g (59%) of pure 4-bromophenylboronic acid remain.
  • the reaction mixture is poured into Er ⁇ cold in about 11 methanol and acidified with 6N hydrochloric acid with stirring. If the carbon dioxide evolution does not start immediately, water is added in portions of 50 ml until a vigorous reaction begins. After the evolution of gas has subsided, the mixture is cooled to 0 ° C. for approximately 24 hours. The polymer collects at 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. For this, the polymer is filled with large amounts of water and ethanol washed. At the same time, ethanol serves as a middle charge since the polymer is not wetted by water at all. Finally, it is dried in vacuo at 70 ° C for 12 hours. The yields are typically 90%.
  • copolymers can be demonstrated by FT-IR spectroscopy (KBr compacts) and 1 3 C solid-state NMR spectroscopy.
  • the FT-IR spectra of different poly (m-phenylene-co-p-phenylene) s are shown in the range from 2000 c ⁇ r 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.
  • 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 elemental analysis (C, H, S). This is the empirical formula for the sulfonated material
  • the carbon content x c (weight fraction), which the elemental analysis provides, is calculated as:
  • the elemental analysis still provides the hydrogen content X H (wt.). This is used to check the calculated values x and y. From x and y the hydrogen content is calculated and with compared to the actually measured value. It applies to X H :
  • 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 0.1 N sodium hydroxide solution. It is then filtered off and washed to neutrality with distilled water, then with methanol and diethyl ether and then dried in vacuo. The material loses its light yellow color and turns into a gray powder. Based on the molecular formula C 6 H 4 . X (S0 3 Na) x * y H 2 0
  • An electrolyte membrane prepared 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 separated by the membrane with platinum electrodes. It is measured with alternating current of frequency 1 kHz. First, the resistance is measured several times without membrane and then several times with membrane and the two mean values are formed. By calculating the difference Rmit - Rohne, the insertion resistance RH.-bi.o of the membrane is calculated.
  • the resistance of the membrane is calculated
  • a comparison measurement with Nafion 117 provides a resistivity of 8.5 ⁇ cm.
  • a piece of a membrane prepared according to measure 4 is dried in a vacuum drying oven for 30 min at 110 ° C and 30O hPa.
  • the mass is 33.3mg.
  • the membrane is then swollen ge in water at room temperature for 30 min.
  • For reweighing the membrane is removed after removal from the water bath briefly with a filter paper of adhering water and weighed quickly. It then swells at 80 ° C for 20 minutes and then at 90 ° C for 30 minutes. Finally, it is again dried for 30 minutes at 110 ° C and 30O hPa. Thereafter, 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

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.
PCT/DE1996/001599 1995-09-21 1996-08-28 Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises Ceased WO1997011099A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP96943846A EP0852071A2 (fr) 1995-09-21 1996-08-28 Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises
JP9512297A JPH11515040A (ja) 1995-09-21 1996-08-28 官能基化されたコポリ（ｍ−フェニレン）に基づく固体重合体電解質

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19535086.3 1995-09-21
DE19535086A DE19535086B4 (de) 1995-09-21 1995-09-21 Verwendung von polymeren Festkörperelektrolyten sowie Verfahren zu deren Herstellung

Publications (3)

Publication Number Publication Date
WO1997011099A2 WO1997011099A2 (fr) 1997-03-27
WO1997011099A9 true WO1997011099A9 (fr) 1997-05-01
WO1997011099A3 WO1997011099A3 (fr) 1997-06-26

Family

ID=7772773

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/DE1996/001599 Ceased WO1997011099A2 (fr) 1995-09-21 1996-08-28 Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises

Country Status (4)

Country Link
EP (1) EP0852071A2 (fr)
JP (1) JPH11515040A (fr)
DE (1) DE19535086B4 (fr)
WO (1) WO1997011099A2 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19612286A1 (de) * 1996-03-28 1997-10-02 Basf Ag Für elektrochemische Zellen geeignete Polymerisate
DE19653484A1 (de) * 1996-12-20 1998-06-25 Fraunhofer Ges Forschung Verfahren zur Herstellung von Membran-Elektroden-Einheiten und eine so hergestellte Membran-Elektroden-Einheit
DE19917813A1 (de) * 1999-04-20 2000-10-26 Siemens Ag Membranelektrolyt für eine Hochtemperatur-Membran-Brennstoffzelle und Verfahren zu seiner Herstellung
JP3607862B2 (ja) 2000-09-29 2005-01-05 株式会社日立製作所 燃料電池
JP3561250B2 (ja) 2001-09-21 2004-09-02 株式会社日立製作所 燃料電池
JP3737751B2 (ja) 2001-12-20 2006-01-25 株式会社日立製作所 燃料電池、それに用いる高分子電解質及びイオン交換性樹脂
FR2843399B1 (fr) * 2002-08-06 2004-09-03 Commissariat Energie Atomique Polymeres de type polyphenylenes, leur procede de preparation, membranes et dispositif de pile a combustible comprenant ces membranes
CN101142257A (zh) 2005-03-17 2008-03-12 帝人株式会社 电解质膜
ATE527314T1 (de) 2006-03-07 2011-10-15 Solvay Advanced Polymers Llc Neue verwendung eines polyarylens in form eines geknickten starren stabes und artikel aus polyarylen in form eines geknickten starren stabes
JP2010070750A (ja) * 2008-08-21 2010-04-02 Sumitomo Chemical Co Ltd ポリマー、高分子電解質及びその用途
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

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TW256843B (fr) * 1992-06-11 1995-09-11 Hoechst Ag
US5403675A (en) * 1993-04-09 1995-04-04 Maxdem, Incorporated Sulfonated polymers for solid polymer electrolytes

Similar Documents

Publication Publication Date Title
EP0574791B1 (fr) Membrane d'électrolyte polymère et procédé pour sa fabrication
DE60202706T2 (de) Monomer mit elektronenziehender und elektronenabgebender Gruppe, und Copolymer und dieses enthaltende protonenleitende Membran
DE102007034753B4 (de) Fluorierte Polymerblöcke für PEM-Anwendungen
DE102009020231B4 (de) Neue Protonenaustauschmembranen für Brennstoffzellenanwendungen
DE69933129T2 (de) Ionenaustauschpolymere
EP1040155B2 (fr) Procede de production d'une membrane utilisee pour faire fonctionner des piles a combustible et des electrolyseurs
DE102009020232B4 (de) Sulfonierte Polyperfluorcyclobutan-Polyphenylen-Polymere für PEM-Brennstoffzellenanwendungen
DE102009020181B4 (de) Sulfonierte Perfluorcyclobutanblockcopolymere und protonenleitende Polymermembranen
DE102006019414B4 (de) Blockcopolymere mit Säuregruppen
DE19535086B4 (de) Verwendung von polymeren Festkörperelektrolyten sowie Verfahren zu deren Herstellung
WO1997011099A9 (fr) Electrolytes solides polymeres a base de copoly(m-phenylene)s fonctionnalises
DE10258175A1 (de) Ein Blockcopolymer zur Verwendung als fester Polymerelektrolyt, eine ionenleitfähige Membran, die aus einem Blockcopolymer gemacht ist, und Verfahren zur Herstellung eines Blockcopolymers
EP1971635A1 (fr) Membrane polymerique conductrice de protons
DE602004013249T2 (de) Sulfoniertes Polymer mit einem Nitrilgruppen enthaltenden hydrophoben Block und feste Polymerelektrolyte
WO2008012222A2 (fr) Composés de polyarylène sulfonés, matériau pour membrane obtenu à partir de ces derniers, procédé de production et d'utilisation desdits composés
DE102004021074A1 (de) Sulfonimid enthaltende Poly(Arylenether) und Poly(Arylenethersulfone), Verfahren zu deren Herstellung und Verwendung derselben
WO1997005191A1 (fr) Electrolytes polymeres et leur procede de production
WO2006094767A1 (fr) Poly(arylenes) sulfones utilises comme polymeres stables a l'hydrolyse et par thermo-oxydation
EP1165216A1 (fr) Polymeres aromatiques sulfones, membrane contenant ces polymeres, leur procede de production et leur utilisation
DE102007034752B4 (de) Polymerblöcke für PEM-Anwendungen
DE3704411A1 (de) Gereckter poly(heteroarylenvinylen)-formling, bei seiner herstellung verwendetes vorlaeufer-polymer, verfahren zu seiner herstellung und diesen enthaltende hochleitfaehige masse
DE112010005036T5 (de) Polyarylen-Ionomermembranen
DE102006019678B4 (de) Triblockcopolymere mit Säuregruppen
DE602004008754T2 (de) Ionenleitfähige polymermaterialien
DE60307614T2 (de) Polyelektrolytmembran, Verfahren zur Produktion und Brennstoffzelle enthaltend diese Polyelektrolytmembran