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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/02—Polyamines
  • C08G73/026—Wholly aromatic polyamines
  • C08G73/0266—Polyanilines or derivatives thereof
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G49/00—Compounds of iron
  • C01G49/0009—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
• • 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
  • C08G61/124—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 nitrogen atom in the ring
• • 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
• • 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
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
  • C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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 OR LIGHT-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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
• • 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
  • Y02E60/13—Energy storage using capacitors

Definitions

• the invention relates to a process for the production of special oxidizing agents which, in mixtures with precursors for the production of conductive polymers, have a high processing time during the polymerization, oxidizing agents obtainable by this process, mixtures containing such special (retarding) oxidizing agents and their use for the production of solid electrolytic capacitors and conductive layers.
• the compound class of the ⁇ conjugated polymers has been the subject of numerous publications in the past decades. They are also called conductive polymers or synthetic. Referred to metals.
• Polymers are polypyrroles, polythiophenes, polyanilines, polyacetylenes, polyphenylenes and poly (p-phenylen-yinylenes).
• Layers of conductive polymers are used in a variety of technical ways. An overview of is in L. Groenendaal, F. Jonas, D. Freitag, H. Pielartzik & J. R. Reynolds, Adv. Mater. 12 (2000) 4SI - 494.
• conductive polymers takes place chemically oxidatively or electrochemically from precursors for the production of conductive polymers such as optionally substituted thiophenes, pyrroles and anilines and their respective optionally oligomeric derivatives.
• chemical oxidative polymerization is widespread because it is technically easy to implement on a variety of substrates.
• the precursors for the production of conductive polymers are polymerized using an oxidizing agent. The polymerization is so fast that • the precursors for the production of conductive polymers and the oxidizing agent usually have to be applied to the substrate one after the other.
• EP-A 339 340 describes the chemically oxidative polymerization of 3,4-disubstituted thiophenes.
• these thiophenes can also be processed into conductive layers in solution in the presence of the oxidizing agent. However, the reaction starts after a few minutes.
• EP-A 615 256 describes that the addition of a non-volatile base such as imidazole can slow down the polymerization in mixtures of oxidizing agent and precursors for the production of conductive polymers. This allows the polymerization to be suppressed for a few hours. However, the additive remains in the conductive layer and can interfere with the function of the layer there. '
• oxidizing agents which can be used together with precursors for the production of conductive polymers at temperatures which are technically easy to handle, the polymerization being suppressed for a sufficiently long time for industrial applications without having to carry out complex further process steps to prevent it. Therefore, the object was to find suitable oxidizing agent for the chemically oxidative polymerisation of precursors for producing conductive polymers and to produce, which suppress the polymerization sufficiently long and with which conductive layers' - can be prepared - for example, solid electrolyte capacitors, or other applications.
• Another task was to find suitable oxidizing agents which are also stable in storage.
• the present invention therefore relates to a process for the production of an oxidizing agent for the production of conductive polymers, characterized in that a metal salt of an organic acid or inorganic acid having organic residues is treated with an ion exchanger.
• radical definitions, parameters and explanations can set out below, with each other so there 'combined between the respective ranges and preferred ranges in any way.
• Inorganic or organic ion exchangers can be used as ion exchangers, but organic ion exchangers are preferred,
• Inorganic anion exchangers are, for example, zeolites, montmorillonites, attapulgites, bentonites and other aluminosilicates, or else acid salts of polyvalent metal ions such as zirconium phosphate, titanium tungstate, nickel hexacyanoferrate (II).
• Organic anion exchangers are, for example, polycondensates, e.g. from phenol and formaldehyde, or polymers, e.g. obtainable by copolymerization from styrene, acrylates or methacrylates and divinylbenzene, which were subsequently functionalized accordingly.
• polycondensates e.g. from phenol and formaldehyde
• polymers e.g. obtainable by copolymerization from styrene, acrylates or methacrylates and divinylbenzene, which were subsequently functionalized accordingly.
• other appropriately functionalized macromolecules for example those of natural origin such as celluloses, dextrans and aragoses, can also be used.
• the preceding enumeration serves as an example and is not to be interpreted as a limitation.
• the ion exchangers can be used in the use forms known to those skilled in the art, for example in the form of pearls, as granules, as powder resins, in ground form, incorporated into fabrics or fibers, as papers, layers or other bodies, in the form of ion exchange membranes, as liquid organic ion exchangers or optionally also used as a magnetic ion exchanger.
• the ion exchangers can be macroporous, microporous or gel-like. Macroporous ion exchangers are preferably used.
• Anion exchangers are preferably used as ion exchangers.
• Anion exchangers have functional basic groups bonded to the ion exchanger, such as primary, secondary or tertiary amine groups or quaternary ammonium groups.
• the basicity of the ion exchangers can vary. For example, contain strongly basic ion exchangers usually quaternary ammonium groups, while weakly basic 'ion exchangers often less basic primary, secondary and / or tertiary amine groups bear. However, any mixed forms are known between strong and weakly basic ion exchangers. Weakly basic anion exchangers are preferred in the sense of the invention.
• Ion exchangers and their preparation are known to the person skilled in the art and are described in the relevant specialist literature, for example in Ullmann's Encyclopedia of Industrial Chemistry (Verlag Chemie, Weinheim), Volume 13, 4th Edition, pp. 281-308. However, all ion exchangers which can be prepared by newer methods and which have the properties listed above are also suitable for carrying out the process according to the invention.
• Suitable ion exchangers are like them, Leverkusen are sold functionalized with tertiary amines macroporous polymers of styrene and divinylbenzene, for example, under the trade name Lewatit ® from Bayer AG.
• the ion exchangers can be used in the process according to the invention without prior treatment. However, it is also possible to treat the ion exchangers with acids such as sulfuric acid or with bases such as sodium hydroxide or potassium hydroxide solution, for example in order to regenerate them before use.
• the ion exchangers used according to the invention can also be subjected to such a regeneration if their capacity has been exhausted to the extent that they are loaded to such an extent that they are not sufficiently interchangeable for the implementation of the method according to the invention. show more. In this way, ion exchangers can be recycled for use in the process according to the invention.
• the metal salts are preferably treated with the ion exchanger in the presence of one or more solvents.
• Treatment can be continuous or discontinuous e.g. by mixing, stirring or shaking and subsequent separation, in a particular embodiment the treatment is carried out continuously.
• a solution of the metal salt passed over a column containing the ion exchanger e.g. Metal salt, solvents and ion exchangers can also be brought together in one container and stored there for a time of, for example, one minute to 72 hours.
• the ion exchanger can e.g. be separated from the oxidizing agent via a filter, a membrane or a centrifuge.
• the process according to the invention can be carried out at temperatures of, for example, -20 ° C. to 120 ° C. Preference is given to temperatures which permit simple and inexpensive industrial implementation, for example temperatures from 10 to 40 ° C., particularly preferably room temperature.
• the amount of ion exchanger added depends on its capacity and the contact time of the metal salt and ion exchanger. If necessary, it can be determined by preliminary tests.
• the amount of ion exchanger is expediently chosen so that the resulting oxidizing agents according to the invention lead to a sufficiently low polymerization rate. Too small amounts of ion exchanger can lead to exhaustion of the ion exchanger before the metal salt has been adequately treated; too short a contact time can lead to incomplete treatment of the metal salt despite sufficient capacity of the ion exchanger. With too high capacities and or long contact times at the ion exchanger, an oxidizing agent can be produced which almost completely suppresses the polymerization at suitable process temperatures.
• the suitable amount of added ion exchanger can, if necessary, be determined by preliminary tests.
• the ion exchangers used can be water-containing or water-free.
• water-containing means a water content of 1% by weight and more.
• commercially available ion exchangers with a commercially available water content of, for example, 30 to 70% by weight are used.
• the water content of the ion exchanger can optionally be reduced before the treatment of the metal salt, for example by rinsing with a solvent or drying. This is particularly advantageous if a solution of an oxidizing agent with a low water content is desired. It has surprisingly been found that solutions of oxidizing agents according to the invention with a low water content are stable in storage under customary storage or transport conditions.
• ion exchangers with such a low water content are therefore used that the solution of the oxidizing agent according to the invention after treatment with the ion exchanger has a water content of 0 to 10% by weight, preferably 0 to 5% by weight. %, particularly preferably from 0 to 2 wt .-%, each based on the total weight of the solution.
• the water content of ion exchangers with a high water content can be e.g. be reduced by gradually or continuously rinsing with an anhydrous solvent or by thermal drying or vacuum drying.
• the same solvent in which the oxidizing agent is dissolved is preferably used as the solvent for rinsing.
• the oxidants according to the invention can also be subsequently reduced in their water content after treatment with the ion exchanger, for example by drying and then dissolving them.
• an anhydrous solvent or by using dehydrating agents such as molecular sieves can also be used.
• solutions of the oxidants according to the invention with a low water content have been found to be stable under normal storage and transport conditions, i.e. they show no precipitations for a period of up to several months.
• Solutions of oxidizing agents according to the invention with an increased water content show, under the same conditions over time, i.e. under certain circumstances precipitations can occur after just a few hours or days.
• the latter solutions of oxidizing agents according to the invention can be cooled to temperatures of 10 ° C. or lower, preferably 6 ° C. or lower, in order to increase the storage stability.
• the advantage of the solutions of the oxidants according to the invention with a low water content compared to solutions of the oxidants according to the invention with a higher water content is consequently that transport and / or storage do not require separate cooling.
• the solutions of the oxidizing agents according to the invention preferably contain 1 to 80% by weight, particularly preferably 10 to 60% by weight, very particularly preferably 15 to 50% by weight of the oxidizing agent according to the invention.
• metal salts known to the person skilled in the art and suitable for the oxidative polymerization of thiophenes, anilines or pyrroles as oxidizing agents can be used as metal salts.
• Preferred transition metal salts are those of iron (Jjr).
• Iron (IU) salts are often inexpensive, readily available and can be handled easily, such as the iron (IH) salts of inorganic acids, such as iron (II [) halide (eg FeCl 3 ) or iron (IIt ) Salts of other inorganic acids, such as Fe (C10) 3 or Fe 2 (S0 4 ) 3 , and the iron (TII) salts of organic acids and organic residues containing organic residues.
• iron (IU) salts of organic residues containing inorganic acids are, for example, the iron (i ⁇ ) salts of the sulfuric acid semiesters of C 1 -C 20 -laols, e.g. called the iron (TI ⁇ ) salt of lauryl sulfate.
• iron (JiI) ⁇ salts of organic acids which may be mentioned are: the iron ( ⁇ i) salts of C 1 -C 2 -alkanesulfonic acids, such as methane, ethane, propane, butane or higher sulfonic acids such as dodecanesulfonic acid, of aliphatic perfluorosulfonic acids , such as trifluoromethanesulfonic acid, perfluorobutanesulfonic acid or perfluorooctanesulfonic acid, from aliphatic C; [ -C20-Cafbonic acids such as 2-ethylhexylcarboxylic acid, of aliphatic perfluorocarboxylic acids such as trifluoroacetic acid or perfluorooctanoic acid, and of aromatic sulfonic acids optionally substituted by C 1 -C 2 -alkyl groups such as benzenesulfonic acid, o-toluen
• One or more alcohol (s), water or a mixture of one or more alcohol (s) and water are preferably used as the solvent or solvents.
• Butanol, ethanol and methanol are particularly preferred among the alcohols.
• the oxidizing agent produced according to the invention can be separated from the solvent after treatment with the ion exchanger and, if appropriate, can be dissolved again in the same or different solvent from the selection listed above.
• the invention furthermore relates to oxidizing agents or solutions of oxidizing agents obtainable by the process according to the invention described above. All apply here Preferred ranges that apply to the process according to the invention, individually and in any combination, also for the oxidizing agents or their solutions obtainable by this process.
• the invention preferably relates to oxidizing agents or solutions of oxidizing agents prepared by the process according to the invention described above.
• the oxidizing agents according to the invention slow down or delay the polymerization - at the same concentration and the same reaction temperature - in reactive mixtures of precursors for the production of conductive polymers and oxidizing agents according to the invention. They are therefore also called retarding oxidizing agents in the following.
• more conductive layers can be produced from the oxidizing agents according to the invention than from oxidizing agents not treated with ion exchangers.
• the retarding (retarding or slowing down) effect of the oxidizing agents according to the invention can be observed in a simple manner, for example, purely optically.
• To determine the retarding effect it is possible, for example, to measure the time in which the first polymer particles are formed, which is visible to the eye.
• the time until visible formation of polymer particles in the reactive mixtures is preferably longer than one hour, particularly preferably longer than 10 hours and very particularly preferably longer than 20 hours.
• the invention therefore relates to the use of the oxidizing agents obtainable by the process according to the invention as retarding oxidizing agents in the oxidative polymerization of precursors for the production of conductive polymers.
• polymers encompasses all compounds with more than one. Repeating unit.
• Conductive polymers are understood here to mean the class of compounds of 7r-conjugated polymers which have an electrical conductivity after oxidation or reduction.
• ⁇ -conjugated polymers are preferably understood to be conductive polymers which have electrical conductivity after oxidation. Examples include his optionally substituted polythiophenes, polypyrroles and polyanilines.
• Preferred conductive polymers for the purposes of the invention are optionally substituted polythiophenes, in particular optionally substituted poly (3,4-ethylenedioxythiophenes).
• Corresponding monomers or their derivatives are accordingly understood as precursors for the production of conductive polymers, hereinafter also referred to as precursors. Mixtures of different precursors can also be used.
• Suitable monomeric precursors are, for example, optionally substituted thiophenes, pyrroles or anilines, preferably optionally substituted thiophenes, particularly preferably optionally substituted 3,4-alkylenedioxythiophenes.
• substituted 3,4-alkylenedioxythiophenes include the compounds of the general ⁇ formula (I) called
• A represents an optionally substituted C 1 -C 5 alkylene radical, preferably an optionally substituted C 2 -C 3 alkylene radical,
• R is a linear or branched, optionally substituted Ci-Cis-alkyl radical, preferably linear or branched, optionally substituted C ⁇ C ⁇ -4 alkyl, optionally substituted C 5 -C ⁇ 2 cycloalkyl, optionally substituted C 6 -C I - Aryl radical, optionally substituted C 7 -C 8 aralkyl radical, optionally substituted C 1 -C 4 hydroxyalkyl radical, preferably optionally substituted C 1 -C 2 hydroxyalkyl radical, or a hydroxyl radical, '
• x represents an integer from 0 to 8, preferably from 0 to 6, particularly preferably 0 or 1,
• radicals R in the event that a plurality of radicals R are bonded to A, these may be the same or different.
• the general formula (I) is to be understood such that the substituent R can be bonded to the alkylene radical A x times.
• Very particularly preferred monomeric precursors are optionally substituted 3,4-ethylenedioxythiophenes.
• substituted 3,4-ethylenedioxythiophenes are the compounds of the general formula (Ia)
• derivatives of these monomeric precursors are understood to mean, for example, dimers or trimers of these monomeric precursors. They are also higher molecular weight derivatives, i.e. Tetramers, pentamers etc. of the monomeric precursors are possible as derivatives.
• the derivatives can be constructed from the same or different monomer units and can be used in pure form and in a mixture with one another and / or with the monomeric precursors. Oxidized or reduced forms of these precursors are also included in the sense of the invention by the term “precursors”, provided that the same conductive polymers are formed in their polymerization as in the precursors listed above.
• C 1 -C 5 -alkylene radicals A are methylene, ethylene, n-propylene, n-butylene or n-pentylene.
• the advantage of applying the oxidizing agent and precursors together for the production of conductive polymers at technically easy-to-use temperatures is that the number of process steps is significantly reduced.
• a defined stoichiometric ratio between the reactants can be set in this way. For example, it is possible to convert the precursors into the polymer in high proportions, possibly even up to almost 100%.
• the solutions or mixtures of the oxidizing agents and the precursors obtainable according to the invention are particularly suitable for producing conductive layers on the surface of porous or smooth substrates. Because the oxidizing agents and the precursors are uniformly distributed in the mixtures, the polymerization also produces homogeneous, ie dense - in the sense of non-porous or not very porous - polymer layers. In the case of sequential application of oxidizing agent and precursors, porous polymer layers arise due to local excess or deficit of oxidizing agent and precursors.
• the conductive layers obtainable from the mixtures according to the invention are therefore distinguished by a particular homogeneity and high conductivity.
• solutions or mixtures according to the invention are accessible for processing for a significantly longer time than those which contain oxidizing agents which have not been treated with an ion exchanger. This makes it possible for the first time to use these mixtures or solutions in continuous, industrial manufacturing processes.
• the invention also relates to mixtures comprising precursors for the production of conductive polymers and one or more oxidizing agents according to the invention and optionally one or more solvents, characterized in that the formation of polymers in the mixtures is delayed compared to untreated oxidizing agents.
• the mixtures according to the invention can be homogeneous or heterogeneous and single or multi-phase.
• the mixtures according to the invention are preferably solutions.
• the oxidizing agents and precursors for the production of conductive polymers can be mixed together as a solid and / or liquid. However, one or more solvents are preferably added to the mixtures. Suitable solvents are above all the solvents already listed above. It is also possible to produce the mixtures directly on the surface to be coated, for example on an oxide layer of a metal or on a substrate surface. For this purpose, oxidizing agents and precursors for the production of conductive polymers are added in succession, preferably in the form of solutions, to the surface to be coated. The mixture is then created by mixing the individual components, i.e. Oxidizing agents and precursors, on the surface to be coated or, if appropriate, after partial or complete evaporation of the solvents by diffusion at the oxidizing agent interface to precursors.
• one or more solvents are preferably added to the mixtures. Suitable solvents are above all the solvents already listed above. It is also possible to produce the mixtures directly on the surface to be coated, for example on an oxide layer of a metal or on
• the mixtures according to the invention can contain water.
• This water can, for example, originate from the oxidizing agent according to the invention or its solution and / or can be added subsequently to the mixtures according to the invention.
• the addition of water can increase the delay in the formation of polymers in the mixtures according to the invention, ie the pot life.
• Additional water is preferably added when using oxidizing agents according to the invention or their solutions with a low water content. 1 to 100% by weight, particularly preferably 1 to 60% by weight, very particularly preferably 1 to 40% by weight, of water, based on the weight of the oxidizing agent according to the invention, are preferably added.
• the conductive polymers produced with the oxidizing agents according to the invention can be neutral or cationic, but they are preferably cationic.
• cationic refers only to the charges which are located on the main polymer chain. These positive charges must be saturated by counterions which, in the special embodiments in which the repeating units are substituted by anionic groups such as, for example, sulfonate or carboxylate groups.
• anionic groups such as, for example, sulfonate or carboxylate groups
• the positive charges of the main polymer chain can be partially or completely saturated by the covalently bound anionic groups. In the event that there are more covalently bound anionic groups than positive charges, a negative total charge of the polymer can also result
• charges are at least 1 and at most p, where p is the total number of all repetition units contained - identical or different - in the polymer.
• the conductive polymers require anions as counterions.
• polymeric carboxylic acids such as polyacrylic acids, polymethacrylic acid or polymalefic acids
• polymeric sulfonic acids such as polystyrene sulfonic acids and polyvinyl sulfonic acids
• polycarbonic and sulfonic acids can also be copolymers of vinylcarbonic and vinylsulfonic acids with other polymerizable monomers, such as acrylic acid esters and styrene.
• the anion of the polystyrene sulfonic acid is particularly preferred as the counter ion.
• the molecular weight of the polyacids providing the polyanions is preferably 1,000 to 2,000,000, particularly preferably 2,000 to 500,000.
• the polyacids or their alkali metal salts are commercially available, for example polystyrene sulfonic 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. 1141 u.fi).
• the monomeric anions such as those used by C ⁇ -C20 alkane sulfonic acids, such as methane, ethane, propane, butane or higher sulfonic acids such as dodecane, of aliphatic perfluorosulfonic acids, such as trifluoromethanesulfonic acid, perfluorobutane sulfonic ⁇ or perfluorooctane sulfonic acid, of aliphatic Ci -C20 carboxylic acids such as 2-ethylhexyl carboxylic acid, of aliphatic perfluorocarboxylic acids such as trifluoroacetic acid or perfluoro-octanoic acid, and of aromatic sulfonic acids optionally substituted by C ⁇ -C20 alkyl groups such as benzenesulfonic acid, o-toluenesulfonic acid, p-toluenesulfonic acid or dodecylbenzene
• the counterions are added to the mixtures, for example in the form of their alkali salts or as free acids.
• the anions present in the oxidizing agent used preferably serve as counterions, so that the addition of additional counterions is not absolutely necessary.
• the mixtures according to the invention can also contain other components such as one or more organic binders which are soluble in organic solvents, such as polyvinyl acetate, polycarbonate, polyvinyl butyrate, polyacrylic acid esters, polymethacrylic acid esters, polystyrene, polyacrylonitrile, polyvinyl chloride, polybutadiene, polyisoprene, polyethers, polyesters, silicones, pyrrole / Acrylic acid ester, vinyl acetate / acrylic acid ester and ethylene / vinyl acetate copolymers or water-soluble binders such as polyvinyl alcohols, crosslinking agents such as polyurethanes or polyurethane dispersions, polyacrylates, polyolefin dispersions, epoxysilanes such as 3-glycidoxypropyltrialkoxysilane, and additives such as, for example surfactants are added.
• organic binders which are soluble in organic solvents, such as polyvinyl a
• oxidizing agents For the oxidative polymerization of the precursors for the production of conductive polymers, 2.25 equivalents of oxidizing agents are theoretically required per mole of thiophene (see, for example, J. Polym. Sc. Part A Polymer Chemistry Vol. 26, p. 1287 (1988)). However, lower or higher equivalents of oxidizing agent can also be used.
• the mixtures preferably contain 1 to 30% by weight of the precursors for the production of conductive polymers and 0 to 50% by weight of binders, crosslinking agents and / or additives, both weight percentages based on the total weight of the mixture.
• the mixtures according to the invention can furthermore contain solvents, counterions, binders and / or crosslinking agents.
• C ⁇ -C2o alkane sulfonic acids such as methane, ethane, propane, butane or higher sulfonic acids such as dodecane sulfonic acid, of aliphatic perfluorosulfonic acids, such as trifluoromethane sulfonic acid, perfluorobutane sulfonic acid or perfiuorooctane sulfonic acid, of aliphatic C -C20 carboxylic acids such as 2-ethylhexylcarboxylic acid, of aliphatic perfluorocarboxylic acids such as trifluoroacetic acid or perfluorooctanoic acid, and of aromatic sulfonic acids optionally substituted by C20 -C20 alkyl groups such as benzenesulfonic acid, o-toluenesulfonic acid, p-toluenesulfonic acid or Dodecylbenzenes
• water preferably 1 to 100% by weight, particularly preferably 1 to 60% by weight, very particularly preferably 1 to 40% by weight of water, based on the weight of the oxidizing agent, is added to the mixtures according to the invention ,
• the “oxidizable metal” preferably forms an anode body with a large surface, for example in the form of a porous sintered body or a roughened foil. In the following, this is also referred to briefly as an anode body.
• the solid electrolyte made of conductive polymer is produced on the anode body covered with an oxide layer by oxidative polymerization of the mixtures described above, by applying these mixtures, preferably in the form of solutions, to the oxide layer of the anode body and the oxidative polymerization, depending on the activity of the one used Oxidizing agent, optionally by heating the coating to the end.
• the anions of the monomeric alkane or cycloalkane sulfonic acids or aromatic sulfonic acids are particularly preferred for use in the electrolytic capacitors according to the invention, since solutions containing them are more suitable for penetrating into the porous anode material and thus a larger contact area can be formed between the anode material and the solid electrolyte.
• the solutions can additionally contain one or more binders, crosslinking agents and / or additives.
• binders Suitable binders, crosslinking agents and / or additives are those listed above for the mixtures according to the invention.
• anode body Depending on the type of anode body, it can be advantageous to impregnate the anode body with the mixtures a further number of times, preferably after washing, in order to achieve thicker polymer layers.
• valve metal is to be understood as those metals whose oxide layers do not allow the current to flow in both directions equally: With an anodically applied voltage, the oxide layers of the valve metals block the current flow, while with cathodically applied voltage large currents occur which destroy the oxide layer can.
• the valve metals include Be, Mg, Al, Ge, Si, Sn, Sb, Bi, Ti, Zr, Hf, V, Nb, Ta and W and an alloy or combination of at least one of these metals with other elements.
• the best known representatives of valve metals are AI, Ta and Nb. Connections with comparable Properties are those with metallic conductivity, which can be oxidized and whose oxide layers have the properties described above.
• NbO has metallic conductivity, but is generally not considered a valve metal.
• layers of oxidized NbO have the typical properties of valve metal oxide layers, so that NbO or an alloy or compound of NbO with other elements are typical examples of such compounds with comparable properties.
• the present invention particularly preferably relates to a method, characterized in that the valve metal or the compound ' with comparable properties is tantalum, niobium, aluminum, titanium, zirconium, hafnium, vanadium, an alloy or compound of at least one of these Metals with other elements, NbO or an alloy or compound of NbO with other elements.
• the “oxidizable metal” preferably forms an anode body with a large surface, for example in the form of a porous sintered body or a roughened foil.
• the present invention therefore also relates to a process for the production of electrically conductive layers, characterized in that the mixtures according to the invention, preferably in the form of solutions, are applied to a base and chemically conductive polymers on this base at temperatures of from -10 ° C. to 250 ° C, preferably at temperatures from 0 ° C to 200 ° C, polymerized.
• spin-coating of the mixtures or solutions is particularly suitable (spin coating).
• counterions can also be added to the solutions. Suitable counterions are those listed above for the mixtures according to the invention, wherein the polyanions can lead to improved film formation properties for the formation of polymer films and are therefore preferred.
• antistatic coatings they can be used, for example, on films, packaging of electronic components, for finishing plastic films and for screen coating. Furthermore, they can be used as cathode materials in capacitors, as transparent electrodes, for example in displays, for example as a replacement for jxidium tin oxide electrodes, or as electrical conductors in polymer electronics. Other applications include sensors, batteries, solar cells, electrochromic windows (smart windows) and 'displays and the corrosion protection.
• the mixtures according to the invention have a significantly longer pot life than the mixture with iron (ILT) -p-toluenesulfonate which has not been treated with an ion exchanger.
• the layer thickness was determined using a Tencor Alpha Step 500 Surface Profiler. The specific conductivity was determined from the surface resistance and layer thickness. The rest of the mixture was stored in a refrigerator at approx. 6 ° C. and the pot life was determined there, as described in Example 1.
• the mixture according to the invention has a significantly longer pot life than the mixture with an oxidizing agent not treated with an ion exchanger. At the same time, the conductivity of the layer is significantly greater and the surface resistance is significantly lower than for the sample which was produced from the reference mixture.
• Example 4
• the pot life of a mixture according to the invention was determined in comparison with a mixture of metal salt not treated with an ion exchanger and with added base.
• Example 2 For this purpose, analogous to Example 1, a 40 wt .-% strength butanolic solution of iron (III) -p-toluene sulfonate in a volume ratio of 2: 1 with the weakly basic anion exchanger Lewatit MP 62 macroporous ® (Bayer AG), and the mixture left for 64 h. The anion exchanger was then filtered off.
• Polymer films could be produced from both of the above mixtures by applying the mixture to a glass plate and drying at 60 ° C.
• the mixture For reference mixtures with larger additives imidazole
• no polymer films could provide more manufacturing • even at temperatures of 150 ° C.
• the mixture according to the invention has a significantly longer pot life than the mixture with an oxidizing agent not treated with an ion exchanger and addition of the base imidazole.
• a second solution was prepared analogously by using a 40 wt .-% ethanolic solution of iron (ITI) -p-toluenesulfonate in the volume ratio 2: basic 1 slightly with that anion exchanger Lewatit macroporous ® MP 62 (Bayer AG) for 7 hours with mixed with a shaker, and then the anion exchanger was filtered off (solution 2).
• a mixture according to the invention consisting of one part by weight of 3,4-ethylenedioxy thiophene (BAYTRON ® M, HC Starck GmbH), 10 parts by weight of solution 1 and 10 parts by weight of solution 2 was prepared, and the mixture in a refrigerator at about 6 ° C stored.
• the pot life was determined analogously to Example 1.
• the pot life was 96 hours.
• the pot life can also be adjusted by mixing differently prepared oxidizing agents according to the invention.
• the pot life of a mixture according to the invention was determined when stored at low temperature.
• Example 2 For this purpose, analogous to Example 1, a 40 wt .-% strength butanolic solution of iron (III) -p-toluene sulfonate in a volume ratio of 2: 1 with the weakly basic anion exchanger Lewatit MP 62 macroporous ® (Bayer AG), and the mixture left for 24 hours. The anion exchanger was then filtered off.
• Analog were mixtures with the ® by the same treatment with the mitt Elba rectangular, macroporous anion exchanger Lewatit MP 64 (Bayer AG) or the. strongly basic, macroporous anion exchanger Lewatit ® MP 600 WS (Bayer AG) prepared as described under a), stored at 6 ° C and the samples also analyzed analogously.
• Example 2 a 40% by weight ethanolic solution of iron (m) - p-toluenesulfonate in a volume ratio of 2: 1 (based on the volume of the ion exchanger before the treatment with ethanol) was used with the weakly basic, macroporous anion exchanger Lewatit ® MP 62 (Bayer AG) mixed for 7 hours with a shaker, and then the anion exchanger was filtered off.
• Figure 2 Comparison of experimental data of the concentration profile of EDT ( ⁇ square), Fe ( ⁇ i) (f diamond) and Fe (LT) (A triangle) at 30 ° C with model simulation (solid lines).

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