WO2010015468A1 - Procédé de production de polythiophènes à l'aide de peroxyde d’hydrogène comme agent oxydant - Google Patents

Procédé de production de polythiophènes à l'aide de peroxyde d’hydrogène comme agent oxydant Download PDF

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WO2010015468A1
WO2010015468A1 PCT/EP2009/058478 EP2009058478W WO2010015468A1 WO 2010015468 A1 WO2010015468 A1 WO 2010015468A1 EP 2009058478 W EP2009058478 W EP 2009058478W WO 2010015468 A1 WO2010015468 A1 WO 2010015468A1
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optionally substituted
general formula
polythiophenes
hydrogen peroxide
polythiophene
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PCT/EP2009/058478
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German (de)
English (en)
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Wilfried Loevenich
Hikmet Karabulut
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H.C. Starck Clevios Gmbh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • C08G61/122—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides
    • C08G61/123—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds
    • C08G61/126—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule derived from five- or six-membered heterocyclic compounds, other than imides derived from five-membered heterocyclic compounds with a five-membered ring containing one sulfur atom in the ring
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/124—Intrinsically conductive polymers
    • H01B1/127—Intrinsically conductive polymers comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/48—Conductive polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/54—Electrolytes
    • H01G11/56—Solid electrolytes, e.g. gels; Additives therein
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • H10K85/113—Heteroaromatic compounds comprising sulfur or selene, e.g. polythiophene
    • H10K85/1135—Polyethylene dioxythiophene [PEDOT]; Derivatives thereof
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/32—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain
    • C08G2261/322—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed
    • C08G2261/3223—Monomer units or repeat units incorporating structural elements in the main chain incorporating heteroaromatic structural elements in the main chain non-condensed containing one or more sulfur atoms as the only heteroatom, e.g. thiophene
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/43—Chemical oxidative coupling reactions, e.g. with FeCl3

Definitions

  • the invention relates to a novel process for the preparation of optionally substituted polythiophenes, in particular of optionally substituted conductive polythiophenes, with the aid of hydrogen peroxide as the oxidizing agent in the presence of a catalyst or enzyme in the absence of inorganic salts.
  • Conductive polymers are increasingly gaining economic importance, since polymers have advantages over metals in terms of processability, weight and the targeted adjustment of properties by chemical modification.
  • Examples of known ⁇ -conjugated polymers are polypyrroles, polythiophenes, polyanilines, polyacetylenes, polyphenylenes and poly (p-phenylenevinylenes).
  • Layers of viable polymers are used in a variety of industrial applications, e.g. as a polymeric counterelectrode in capacitors, as corrosion protection or for through-connection of electronic printed circuit boards.
  • the production of conductive polymers takes place chemically or electrochemically oxidatively from precursors, such as. B.
  • polythiophene is the poly (ethylene-3,4-dioxythiophene) (PEDOT or PEDT) described, for example, in EP 339 340 A2, which is obtained by chemical polymerization of ethylene-3,4-dioxythiophene (EDOT or EDT). which has high conductivities in its oxidized form.
  • PEDOT or PEDT poly(ethylene-3,4-dioxythiophene)
  • EDOT or EDT ethylene-3,4-dioxythiophene
  • 3,4-dioxythiophene) derivatives in particular poly (ethylene-3,4-dioxythiophene) derivatives, their monomeric building blocks, syntheses and applications are L. Groenendaal, F, Jonas, D. Freitag, H. Pielartzik & JR Reynolds , Adv. Mater. 12, (2000) p. 481-494.
  • Dispersions of PEDOT with polystyrenesulfonic acid (PSS), as disclosed, for example, in EP 0440 957 B, have particular technical significance. From these dispersions, it is possible to produce transparent, conductive films which have found a multiplicity of applications, for example as an antistatic coating or as a hole injection layer in organic light-emitting diodes.
  • ferric salts of inorganic acids such as FeCl 3
  • ferric salts of organic acids and acids having organic radicals for example, the iron-OI salts of sulfuric acid half-esters of CpCio alkanols, such as the Fe III Salt of lauryl sulfate pointed.
  • K 2 Cr 2 O 7 alkali and ammonium peroxodisulfates, such as sodium or Kaliumperoxodis ⁇ lfat, alkali metal perborates, potassium permanganate, copper salts, such as copper tetrafluoroborate or cerium (FV) salts or CeO 2 as an oxidizing agent called.
  • EP 0340 512 B describes the preparation of a solid electrolyte from 3,4-ethylene-1,2-dioxythiophene and the use of a cationic polymer prepared by oxidative polymerization as a solid electrolyte in electrolytic capacitors.
  • Poly (3,4-ethylenedioxythiophene) as a replacement of manganese dioxide or of charge transfer complexes in solid electrolytic capacitors reduces the equivalent series resistance of the capacitor due to the higher electrical conductivity and improves the frequency behavior.
  • the oxidizing agents described are the same oxidizing agents which are disclosed in EP 0440 957 B. Again, the reaction products of the oxidants remain in the condenser, and must be washed out in an additional step.
  • Another suitable oxidizing agent for the polymerization of EDOT is hydrogen peroxide, for example, in EP 0440 957 B or EP 1 323 764 A1;
  • hydrogen peroxide leads to an over-oxidation of PEDOT and thus to the destruction of its electrical conductivity, so that hydrogen peroxide is used for structuring PEDOT films (Adv. Mater. 2006, 18 (10), 1307-1312).
  • this polymerization succeeds when in addition the enzyme horseradish peroxidase is used in the presence of sodium polystyrenesulfonate and hydrochloric acid. In this way films with a moderate conductivity of 2 ⁇ 10 -3 S / cm can be produced.
  • a disadvantage of this synthesis is that the polymerization is carried out in the presence of inorganic salts. If the reaction products of these salts are not removed, there is an impairment of the corresponding films in terms of morphology, conductivity and transparency. Upon removal of these reaction products from the dispersion, for example, by the use of an ion exchanger such as EPl 323764 Al described, an additional step is required.
  • a terthiophene is started (Macromolecules, 2008, 41, 3049).
  • the synthesis is carried out using hydrogen peroxide as the oxidizing agent and soybean peroxidase as a catalyst in the presence of Natriuropolystyroisulfonat.
  • a disadvantage of this synthesis is that it is carried out in the presence of sodium ions and a C ⁇ trat buffer, wherein the presence of these minor components leads to an impairment of the films in terms of morphology, conductivity and transparency.
  • only moderate conductivities can be achieved with this method of synthesis.
  • no pure PEDOT is produced because terthiophene is incorporated into the PEDOT polymer chain.
  • PEDOT has proven to be particularly stable over other thiophenes in its oxidized form (L. Groenendaal, Adv. Mat. 2003, 15, 855).
  • the object was therefore to provide such a method.
  • the invention thus provides a process for preparing an optionally substituted polythiophene with hydrogen peroxide as the oxidant in the presence of a catalyst or enzyme, characterized in that the sum of the concentrations of inorganic ions in the reaction mixture is less than 0.05 mol / L.
  • R 1 and R 2 are each independently H, an optionally substituted Cj-Cjg-alkyl radical or an optionally substituted Ci-Cjs-AIkoxyrest, or
  • R 1 and R 2 together represent an optionally substituted C r C r alkylene radical in which one or more C atom (s) may be replaced by one or more identical or different heteroatoms selected from O or S, preferably a Q-Cg - Dioxyalkylenrest, an optionally substituted Ci-Cg-Oxythiaalkylenrest or an optionally substituted Cj-Q-Dithiaalkylenrest, or an optionally substituted d-Cg-AIkylidenrest, wherein optionally at least one C-atom may be replaced by a heteroatom selected from O or S. , stand,
  • R 1 and R 2 have the meaning given for the general formula (I) can be prepared.
  • optionally substituted polythiophenes containing recurring units of the general formula (I) are those containing recurring units of the general formula (I-a) and / or the general formula (I-b)
  • A is an optionally substituted C 1 -C 5 -alkylene radical : preferably an optionally substituted C 2 -C 3 -alkylene radical, Y stands for O or S,
  • R is a linear or branched, optionally substituted Ci-Cig-alkyl radical, preferably linear or branched, optionally substituted is an optionally substituted Cs-C ⁇ -Cycloalkyiresl, an optionally substituted C 6 - C 4 -aryl radical, an optionally substituted Cv-Cig-aralkyl radical, an optionally substituted C r GrHydroxyalkylrest or a hydroxyl radical,
  • x is an integer from 0 to 8, preferably 0, 1 or 2, more preferably 0 or 1, and
  • radicals R are attached to A, they may be the same or different.
  • polythiophenes can be prepared by oxidative polymerization of thiophenes of the general formula (II-a) and / or (II-b) s
  • optionally substituted polythiophenes containing recurring units of the general formula (I) are those containing recurring
  • R and x have the abovementioned meaning.
  • optionally substituted polythiophenes containing recurring units of the general formula (I) are those containing polythiophenes of the general formula (I-aaa) and / or the general formula (I ⁇ aba)
  • the prefix poly-I means that more than one identical or different repeating unit is contained in the polythiophene.
  • the polythiophenes contain a total of n repeating units of the general formula (I), where n can be an integer from 2 to 2000, preferably 2 to 100.
  • the repeating units of general formula (I) may be the same or different within each polythiophene. Preference is given to polythiophenes containing in each case identical recurring units of the general formula (I).
  • the polythiophenes preferably carry H.
  • the polythiophene having repeating units of the general formula (I) is poly (3,4-ethylenedioxythiophene), poly (3,4-ethyleneoxythiathiophene) or poly (thieno [3,4-b] thiophene, ie a homopolythiophene repeating units of the formula (I-aa), (I-aba) or (Ib), wherein in the formula (Ib) Y is S.
  • the polylhiophene having repeating units of the general formula (I) is a copolymer of recurring units of the formula (I-aaa) and (I-aba), ( ⁇ -aaa) and (Ib), (I-aba ) and (Ib) or ( ⁇ -aaa), (I-aba) and (Ib), wherein copolymers of recurring units of the formula (I-aaa) and (I-aba) and (I-aaa) and ( Ib) are preferred.
  • Ci-Cs-Aükylenreste A are within the scope of the invention, methylene, ethylene, n-propylene, n-butylene or n-pentylene, C r C 8 -AIkyIenreste additionally n ⁇ hexylene, n-heptylene and n-octylene.
  • C 1 -C 8 -alkylidene radicals in the context of the invention are Ci-Cg-alkylene radicals having at least one double bond and listed above.
  • Cj-Cg-Dioxyalkylenreste, CRCG-Oxythiaalky ⁇ enreste and C etc. - Q Dithiaalkylenreste are in the context of the invention for the Q detailed above
  • Q-Qs-alkoxy radicals are in the context of the invention for the alkoxy radicals corresponding to the above-mentioned Q-Qg-alkyl radicals.
  • the preceding list serves to exemplify the invention and is not to be considered as exhaustive.
  • the polythiophenes may be neutral or cationic. In preferred embodiments they are cationic, with “cationic” referring only to the charges which are located on the polythiophene main chain
  • the polythiophenes can carry positive and negative charges in the structural unit, the positive charges on the polythiophene main chain and the negative charges are optionally present on the radicals R substituted by sulfonate or carboxylate groups, whereby the positive charges of the polythiophene main chain can be partially or completely saturated by the optionally present anionic groups on the radicals R.
  • the polythiophenes can be cationic, neutral or even anionic in these cases
  • the positive charges on the poly Thiophensburgkette are relevant.
  • the positive charges are not shown in the formulas because their exact number and position can not be determined properly. However, the number of positive charges is at least 1 and at most n, where n is the total number of all repeating units (equal or different) within the polythiophene.
  • the cationic polythiophenes require anions as counterions.
  • Suitable counterions are monomeric or polymeric anions, the latter also referred to below as polyanions.
  • Preferred polymeric anions are, for example, anions of polymeric carboxylic acids, such as polyacrylic acids, polymethacrylic acids or polymaleic acids, or polymeric sulfonic acids, such as polystyrenesulfonic acids and polyvinylsulfonic acids.
  • polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acids or polymaleic acids
  • polymeric sulfonic acids such as polystyrenesulfonic acids and polyvinylsulfonic acids.
  • These polycarboxylic and sulfonic acids may also be copolymers of vinyl carboxylic and vinyl sulfonic acids with other polymerizable monomers such as acrylic acid esters and styrene.
  • acrylic acid esters and styrene such as acrylic acid esters and styrene.
  • These may, for example, also be partially fluorinated or perfluorinated polymers containing SO 3 H or COOH groups.
  • polystyrene sulfonic acid PSS
  • PSS polystyrene sulfonic acid
  • the molecular weight of the polyanionic polyacids is preferably 1,000 to 2,000,000, more preferably 2,000 to 500,000.
  • the polyacids or their alkali salts are commercially available, e.g. Polystyrenesulfonic acids and polyacrylic acids, or else can be prepared by known processes (see, for example, Houben Weyl, Methods of Organic Chemistry, Vol. E 20 Macromolecular Substances, Part 2, (1987), p.
  • Examples of monomeric anions are those of C 1 -C 20 -alkanesulfonic acids, such as methane, etane, propane, butane or higher sulfonic acids, such as dodecanesulfonic acid, of a-aliphatic perfluorosulfonic acids, such as trifluoromethanesulfonic acid, perfluorobutanesulfonic acid or perfluorooctanesulfonic acid, aliphatic CrC 20 carboxylic acids such as 2-
  • Ethylhexylcarboxylic acid aliphatic perfluorocarboxylic acids, such as trifluoroacetic acid or perfluorooctanoic acid, and aromatic, optionally substituted by C r C 2 o-Alkylgru ⁇ pen sulfonic acids such as benzenesulfonic acid, o-toluenesulfonic acid 5 p-ToluoIsulfonklare, dodecylbenzenesulfonic acid, dinonylnaphthalenesulfonic acid or dinonylnaphthalenedisulfonic acid, and of cycloalkanesulfonic acids such as camphorsulfonic acid or tetrafluoroborates, hexafluorophosphates, perchlorates, hexafluoroantimonates, hexafluoroarsenates or hexachloroantimonals.
  • anions of p-toluenesulfonic acid, methanesulfonic acid or camphorsulfonic acid are particularly preferred.
  • Cationic polythiophenes which contain anions as counterions for charge compensation are also often referred to in the art as polythiophene / (poly) anion complexes.
  • Preferred thiophenes of the general formula (II-a) are those of the general formula (II-a-1) and / or (II-a-2)
  • thiophenes of the general formula (II-a) are those of the general
  • derivatives of the thiophenes listed above are understood as meaning, for example, dimers or trimers of these thiophenes.
  • the derivatives can be constructed from the same or different monomer units and can be used in pure form and mixed with one another and / or with the abovementioned thiophenes.
  • Oxidized or reduced forms of these thiophenes and thiophene derivatives are also included within the meaning of the invention by the term thiophenes and thiophene derivatives, provided that the same conductive polymers are formed during their polymerization as in the thiophenes and thiophene derivatives listed above.
  • Processes for the preparation of the thiophenes and their derivatives are known to the person skilled in the art and are described, for example, in L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik & JR Reynolds, Adv. Mater. 12 (2000) 481-494 and references cited therein.
  • Suitable solvents which may be mentioned are, in particular, the following organic solvents which are inert under the reaction conditions: aliphatic alcohols, such as methanol, ethanol, isopropanol and butanol; aliphatic ketones such as acetone and methyl ethyl ketone; aliphatic carboxylic acid esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xyloi; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; Chlorinated hydrocarbons such as dichloromethane and dichloroethane; aliphatic nitriles such as acetonitrile, aliphatic sulfoxides and
  • Sulfones such as dimethylsulfoxide and sulfolane; aliphatic carboxylic acid amides such as methylacetamide, dimethylacetamide and dimethylformamide; aliphatic and araliphatic ethers such as diethyl ether and anisole.
  • water or a mixture of water with the aforementioned organic solvents may also be used as the solvent.
  • Preferred solvents are alcohols and water and mixtures containing alcohols or water or mixtures of
  • Thiophenes which are liquid under the oxidation conditions, can also be polymerized in the absence of solvents.
  • inorganic or organic compounds which catalyze the use of hydrogen peroxide as the oxidizing agent can be used as catalyst or enzyme.
  • Preferred compounds are peroxidases as enzymes, such as cytochrome C peroxidase, horseradish peroxidase or thyroid peroxidase.
  • the prosthetic groups of the enzymes for example the heme group.
  • organic complexes of metal ions such as metalloporphorin complexes or metallophthalocyanine complexes (J. Mat. Chem. 2008, 18, 573-578). Particularly preferred is horseradish peroxidase and
  • Soybean peroxidase used.
  • inorganic ions are understood as meaning those ions which contain no carbon atoms.
  • H + and OH " are likewise not counted among the inorganic ions in the sense of this invention, meaning that all cations of the metals such as Lf 5 Na + , K + , Mg 2+ and Fe 3+ belong to the inorganic cations include, for example, F " , Cl, Br “ , ClO 4 " and SO 4 2" .
  • the sum of the concentrations of inorganic ions in the reaction mixture is less than 0.04 mol / L, more preferably less than 0.03 mol / L, and most preferably less than 0.02 mol / L.
  • the fields of application of the optionally substituted polythiophenes which can be prepared by the process according to the invention are many.
  • stable dispersions or solutions comprising optionally substituted polythiophenes of the general formula (I) and a counterion or else directly conducting layers containing such polythiophenes have been prepared, in which case a large number of further compounds are used
  • dispersions or solutions are characterized by being stable, i. these dispersions or solutions may be stored for at least 3 days, preferably for more than 30 days at room temperature, without changing the properties, such as the conductivity, of these dispersions or solutions.
  • another object of the present invention are dispersions or solutions prepared by the inventive method.
  • a still further object of the present invention are conductive layers comprising dispersions or solutions prepared by the process of the present invention.
  • these conductive layers containing optionally substituted polythiophenes are polymerized, optionally substituted thiophenes or thiophene derivatives are polymerized with hydrogen as the oxidant in the presence of a catalyst or enzyme on a suitable substrate.
  • the concentration of inorganic ions in the reaction mixture is less than 0.05 mol / l.
  • the abovementioned substrate may be, for example, glass, glass (flexible glass) or plastics to be coated in the form of shaped bodies or films and other shaped bodies to be coated, for example anodes of
  • Capacitors act.
  • Comparative Example 1 Preparation of a PBDT: PSS dispersion with the aid of hydrogen peroxide in the presence of an enzyme and inorganic salts
  • the comparative example was prepared according to Rumbau et al. (Biomacromolecules, Vol. 8 (2), 2007, p. 315).
  • the mixture thus contains concentrations of 0.05 mol / L sodium ions and 0.07 mol / L CMO ions.
  • a PET film was ozonized to determine the surface resistance.
  • a film of the above-described mixture was prepared with a 24 ⁇ m doctor blade, and this film was dried at 130 ° C. for 5 minutes (min.). The surface resistance was determined using a 4 point meter and was 5.5 x 10 8 ohms / square.
  • the above mixture was allowed to stand at room temperature for 3 days; then this preparation was again doctored in the same manner as described above and the surface resistivity was again determined.
  • the SAW was now 1 x 10 9 ohms / square.
  • Example 1 (according to the invention): Preparation of a PEDT: PSS dispersion with the aid of hydrogen peroxide in the presence of a catalyst and in the absence of salts
  • HRP horseradish peroxidase
  • a PET film was also ozonized to determine the SAW. Subsequently, a film of the above-described mixture was prepared with a 24 ⁇ m doctor blade and this
  • the OFW was determined by means of a 4-point measuring device and was 4 x 10 4 ohms / square.
  • the anion content of the solution was determined by ion chromatography. Cation content was determined by ICP (Inductively Coupled Plasma) atomic spray microscopy:
  • a cleaned glass substrate was placed on a spin coater and 10 ml of the above solution / dispersion were spread on the substrate 24 hours after preparation. Subsequently, the supernatant solution was spun off by rotation of the plate. Thereafter, the thus coated substrate was dried for 15 minutes at 200 ° C. on a hot plate.
  • the layer thickness was
  • the conductivity was determined by evaporating over a shadow mask Ag electrodes 2.5 cm in length at a distance of 10 mm.
  • the surface resistance determined with an electrometer (Keithly 614) was multiplied by the layer thickness to obtain the electrical resistivity.
  • the resistivity of the layer was 3.7 ohm-cm.
  • the conductivity was 0.27 S / cm.
  • Example 2 In-s ⁇ tu polymerization of EDT with the aid of hydrogen peroxide in the presence of an enzyme and in the absence of salts
  • Ethylenedioxythiophene (1.6 g, 11.2 mmol, Cievios M V2, HCStarck GmbH) and p-toluenesulfonic acid (1.06 g, 5.6 mmol) were dissolved in a mixture of 10 g of water and 10 g of isopropanol , 120 mg of horseradish peroxidase (HRP, ECL I I .1.7 type II, Aldrich) was dissolved in 5 g of water and added. This mixture was cooled to 4 ° C. Then, 2.4 g of a 30% hydrogen peroxide solution was added, and this mixture was stirred for 5 minutes.
  • HRP horseradish peroxidase
  • the OFW was determined: 700 k ⁇ / square.
  • Example 3 use of one with hydrogen peroxide in the absence of
  • Salts produced PEDTrPSS layer as a polymeric counter electrode in capacitors
  • Capacitor anodes were made of tantalum powder (type VFI-70KD, HCStarck GmbH) and formed at 20 V and 150 mA / g in a H 3 PO 4 solution with the conductivity 4300 ⁇ S at 85 0 C, so that on the porous sintered anode forms an electrochemically generated oxide layer.
  • Ethylenedioxythiophene (1.6 g, 11 mmol, HC Starck GmbH, Clevios M V2) was dissolved in 10 g of water and 10 g of isopropanol. Then, p-toluenesulfonic acid (1.06 g, 6 mmol, Aidrich) was added. The mixture was cooled to 4 ° C and stirred. A solution of horseradish peroxidase (120 mg, peroxidase EORP, EC 1.11.1.7 type II, Aidrich) was dissolved in 5 g of water (5.0 g) and added followed by stirring for 0 min. Then, 2.4 g of a 30% hydrogen peroxide solution was added, and this mixture was stirred for 5 minutes.
  • the tantalum anodes were immersed in the solution thus prepared for 60 seconds and stored at room temperature for 15 minutes. Thereafter, they were dipped in the polymerization solution again for 60 seconds and then dried at room temperature for four hours. Finally, the capacitor anodes were dried at 100 ° C. for 30 minutes in a drying oven. To be able to electrically contact the capacitor anodes, an outer layer consisting of an ethylene dioxythiophene-based conductive polymer dispersion was applied to the anode. The external contacting was completed first with a graphite layer and then with a silver layer.
  • the capacitance and equivalent series resistance (ESR) of the anodes were determined by the four-point technique used in metrology using an LCR meter (Agilent 4284A), measuring capacitance at 120 Hz and ESR at 100 kHz.
  • the capacitance was 13 ⁇ F; the median (out of nine anodes) of the ESR was measured to be 702 m ⁇ .

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Abstract

La présente invention concerne un nouveau procédé de production de polythiophènes éventuellement substitués, notamment de polythiophènes conducteurs, à l'aide de peroxyde d’hydrogène comme agent oxydant en présence d’un catalyseur ou d’une enzyme et de préférence en l’absence de sels inorganiques.
PCT/EP2009/058478 2008-08-06 2009-07-06 Procédé de production de polythiophènes à l'aide de peroxyde d’hydrogène comme agent oxydant WO2010015468A1 (fr)

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US8094434B2 (en) 2008-04-01 2012-01-10 Avx Corporation Hermetically sealed capacitor assembly
US8194395B2 (en) 2009-10-08 2012-06-05 Avx Corporation Hermetically sealed capacitor assembly
EP2462898A1 (fr) * 2010-12-09 2012-06-13 Université de Liège Composite comportant des nanoparticules et procédé de fabrication de nanoparticules
US8279584B2 (en) 2010-08-12 2012-10-02 Avx Corporation Solid electrolytic capacitor assembly
US8300387B1 (en) 2011-04-07 2012-10-30 Avx Corporation Hermetically sealed electrolytic capacitor with enhanced mechanical stability
US8379372B2 (en) 2011-04-07 2013-02-19 Avx Corporation Housing configuration for a solid electrolytic capacitor
US8451588B2 (en) 2011-03-11 2013-05-28 Avx Corporation Solid electrolytic capacitor containing a conductive coating formed from a colloidal dispersion
US8493713B2 (en) 2010-12-14 2013-07-23 Avx Corporation Conductive coating for use in electrolytic capacitors
US8576543B2 (en) 2010-12-14 2013-11-05 Avx Corporation Solid electrolytic capacitor containing a poly(3,4-ethylenedioxythiophene) quaternary onium salt
US8848342B2 (en) 2010-11-29 2014-09-30 Avx Corporation Multi-layered conductive polymer coatings for use in high voltage solid electrolytic capacitors
US8947857B2 (en) 2011-04-07 2015-02-03 Avx Corporation Manganese oxide capacitor for use in extreme environments
US8971019B2 (en) 2012-03-16 2015-03-03 Avx Corporation Wet capacitor cathode containing an alkyl-substituted poly(3,4-ethylenedioxythiophene)
US9214285B2 (en) 2012-04-11 2015-12-15 Avx Corporation Solid electrolytic capacitor with enhanced mechanical stability under extreme conditions
US9224541B2 (en) 2010-11-01 2015-12-29 Avx Corporation Solid electrolytic capacitor for use in high voltage and high temperature applications
US9324503B2 (en) 2013-03-15 2016-04-26 Avx Corporation Solid electrolytic capacitor
US9472350B2 (en) 2013-05-13 2016-10-18 Avx Corporation Solid electrolytic capacitor containing a multi-layered adhesion coating
US9754730B2 (en) 2015-03-13 2017-09-05 Avx Corporation Low profile multi-anode assembly in cylindrical housing
US9767964B2 (en) 2011-04-07 2017-09-19 Avx Corporation Multi-anode solid electrolytic capacitor assembly
US9824826B2 (en) 2013-05-13 2017-11-21 Avx Corporation Solid electrolytic capacitor containing conductive polymer particles
US9865401B2 (en) 2012-08-30 2018-01-09 Avx Corporation Method for manufacturing solid electrolytic capacitor, and solid electrolytic capacitor
US9892862B2 (en) 2013-05-13 2018-02-13 Avx Corporation Solid electrolytic capacitor containing a pre-coat layer
US9928963B2 (en) 2015-03-13 2018-03-27 Avx Corporation Thermally conductive encapsulant material for a capacitor assembly
US10014108B2 (en) 2015-03-13 2018-07-03 Avx Corporation Low profile multi-anode assembly
US10297393B2 (en) 2015-03-13 2019-05-21 Avx Corporation Ultrahigh voltage capacitor assembly
US11081288B1 (en) 2018-08-10 2021-08-03 Avx Corporation Solid electrolytic capacitor having a reduced anomalous charging characteristic
US11380492B1 (en) 2018-12-11 2022-07-05 KYOCERA AVX Components Corporation Solid electrolytic capacitor
US11756742B1 (en) 2019-12-10 2023-09-12 KYOCERA AVX Components Corporation Tantalum capacitor with improved leakage current stability at high temperatures
US11763998B1 (en) 2020-06-03 2023-09-19 KYOCERA AVX Components Corporation Solid electrolytic capacitor

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US8094434B2 (en) 2008-04-01 2012-01-10 Avx Corporation Hermetically sealed capacitor assembly
US8576544B2 (en) 2008-04-01 2013-11-05 Avx Corporation Hermetically sealed capacitor assembly
US8194395B2 (en) 2009-10-08 2012-06-05 Avx Corporation Hermetically sealed capacitor assembly
US8279584B2 (en) 2010-08-12 2012-10-02 Avx Corporation Solid electrolytic capacitor assembly
US9224541B2 (en) 2010-11-01 2015-12-29 Avx Corporation Solid electrolytic capacitor for use in high voltage and high temperature applications
US8848342B2 (en) 2010-11-29 2014-09-30 Avx Corporation Multi-layered conductive polymer coatings for use in high voltage solid electrolytic capacitors
EP2462898A1 (fr) * 2010-12-09 2012-06-13 Université de Liège Composite comportant des nanoparticules et procédé de fabrication de nanoparticules
WO2012076288A1 (fr) * 2010-12-09 2012-06-14 Universite De Liege Nanoparticules comprenant un composite et procédé de fabrication des nanoparticules
US8493713B2 (en) 2010-12-14 2013-07-23 Avx Corporation Conductive coating for use in electrolytic capacitors
US8576543B2 (en) 2010-12-14 2013-11-05 Avx Corporation Solid electrolytic capacitor containing a poly(3,4-ethylenedioxythiophene) quaternary onium salt
US8451588B2 (en) 2011-03-11 2013-05-28 Avx Corporation Solid electrolytic capacitor containing a conductive coating formed from a colloidal dispersion
US9508492B2 (en) 2011-04-07 2016-11-29 Avx Corporation Manganese oxide capacitor for use in extreme environments
US8379372B2 (en) 2011-04-07 2013-02-19 Avx Corporation Housing configuration for a solid electrolytic capacitor
US8947857B2 (en) 2011-04-07 2015-02-03 Avx Corporation Manganese oxide capacitor for use in extreme environments
US10658123B2 (en) 2011-04-07 2020-05-19 Avx Corporation Multi-anode solid electrolytic capacitor assembly
US10014120B2 (en) 2011-04-07 2018-07-03 Avx Corporation Manganese oxide capacitor for use in extreme environments
US8300387B1 (en) 2011-04-07 2012-10-30 Avx Corporation Hermetically sealed electrolytic capacitor with enhanced mechanical stability
US9767964B2 (en) 2011-04-07 2017-09-19 Avx Corporation Multi-anode solid electrolytic capacitor assembly
US9218913B2 (en) 2012-03-16 2015-12-22 Avx Corporation Wet capacitor cathode containing an alkyl-substituted poly(3,4-ethylenedioxythiophene)
US8971019B2 (en) 2012-03-16 2015-03-03 Avx Corporation Wet capacitor cathode containing an alkyl-substituted poly(3,4-ethylenedioxythiophene)
US9214285B2 (en) 2012-04-11 2015-12-15 Avx Corporation Solid electrolytic capacitor with enhanced mechanical stability under extreme conditions
US9865401B2 (en) 2012-08-30 2018-01-09 Avx Corporation Method for manufacturing solid electrolytic capacitor, and solid electrolytic capacitor
US9324503B2 (en) 2013-03-15 2016-04-26 Avx Corporation Solid electrolytic capacitor
US9824826B2 (en) 2013-05-13 2017-11-21 Avx Corporation Solid electrolytic capacitor containing conductive polymer particles
US9892862B2 (en) 2013-05-13 2018-02-13 Avx Corporation Solid electrolytic capacitor containing a pre-coat layer
US9472350B2 (en) 2013-05-13 2016-10-18 Avx Corporation Solid electrolytic capacitor containing a multi-layered adhesion coating
US9928963B2 (en) 2015-03-13 2018-03-27 Avx Corporation Thermally conductive encapsulant material for a capacitor assembly
US10014108B2 (en) 2015-03-13 2018-07-03 Avx Corporation Low profile multi-anode assembly
US10297393B2 (en) 2015-03-13 2019-05-21 Avx Corporation Ultrahigh voltage capacitor assembly
US9754730B2 (en) 2015-03-13 2017-09-05 Avx Corporation Low profile multi-anode assembly in cylindrical housing
US11081288B1 (en) 2018-08-10 2021-08-03 Avx Corporation Solid electrolytic capacitor having a reduced anomalous charging characteristic
US11380492B1 (en) 2018-12-11 2022-07-05 KYOCERA AVX Components Corporation Solid electrolytic capacitor
US11756742B1 (en) 2019-12-10 2023-09-12 KYOCERA AVX Components Corporation Tantalum capacitor with improved leakage current stability at high temperatures
US11763998B1 (en) 2020-06-03 2023-09-19 KYOCERA AVX Components Corporation Solid electrolytic capacitor

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