High-purity sulfonated thiophene monomer

Abstract

The present invention relates to a compound of structure (I), 1 and X 2 each independently represents O or S, and X 3 is R 1 represents -CH2-O- having a carbon atom bonded to 1 represents a trivalent organic group, and R 2 represents a divalent organic group, M 1 represents a monovalent cation), wherein the monomer composition comprises at least one functionalized thiophene monomer having structure (II): 3 represents a divalent organic group, M 2 represents a monovalent cation), or the monomer composition comprises an unsaturated organic sulfonic acid having structure (II) in a maximum amount such that the molar ratio of the total amount of unsaturated organic sulfonic acids having structure (II) to the total amount of functionalized thiophene monomers having structure (I) is not greater than 1:32. The present invention also relates to a method for preparing a functionalized π-conjugated polythiophene, a functionalized π-conjugated polythiophene obtainable by the method, a polymer composition comprising the functionalized π-conjugated polythiophene, a method for preparing a laminate, a laminate obtainable by the method, and the use of the monomer composition or polymer composition according to the present invention for the preparation of a conductive layer in an electronic device.

Description

[Technical Field]

[0001] The present invention relates to a monomer composition comprising a functionalized thiophene monomer, a method for preparing a functionalized π-conjugated polythiophene, a functionalized π-conjugated polythiophene obtainable by the method, a polymer composition comprising the functionalized π-conjugated polythiophene, a method for preparing a laminate, a laminate obtainable by the method, and the use of the monomer composition or polymer composition according to the invention for the preparation of a conductive layer in an electronic device.

[0002] Commercially available electrolytic capacitors are typically constructed from porous metal electrodes, an oxide layer on the metal surface that functions as a dielectric, a typically solid electrically conductive material introduced into the porous structure, an external electrode (contact), such as a silver layer, additional electrical contacts, and a seal. A frequently used electrolytic capacitor is the tantalum electrolytic capacitor, in which the anode electrode is made of the valve metal tantalum, on which a uniform dielectric layer of tantalum pentoxide is formed by anodization (also called "forming"). A liquid or solid electrolyte forms the capacitor's cathode. Aluminum capacitors are even more frequently used, in which the anode electrode is made of the valve metal aluminum, on which a uniform, electrically insulating aluminum oxide layer is formed as a dielectric by anodization. Again, a liquid or solid electrolyte forms the capacitor's cathode. Aluminum capacitors are typically constructed as wound or stacked capacitors.

[0003] Due to their high electrical conductivity, π-conjugated polymers are particularly suitable as solid electrolytes in the aforementioned capacitors. π-conjugated polymers are also called conductive polymers or synthetic metals. Because polymers offer advantages over metals in terms of processability, weight, and targeted adjustment of properties through chemical modification, π-conjugated polymers are becoming increasingly economically important. Examples of known π-conjugated polymers are polypyrrole, polythiophene, polyaniline, polyacetylene, polyphenylene, and poly(p-phenylene-vinylene). A particularly important polythiophene used industrially is poly(3,4-ethylenedioxythiophene) (PEDOT), due to its extremely high electrical conductivity in its oxidized form.

[0004] Solid electrolytes based on conductive polymers can be applied to oxide layers in various ways. For example, EP 0 340 512 A describes the preparation of a solid electrolyte from 3,4-ethylenedioxythiophene and its use in electrolytic capacitors. According to the teachings of this publication, 3,4-ethylenedioxythiophene is polymerized in situ on the oxide layer. In addition to in situ polymerization, methods for preparing solid electrolytes in capacitors are also known in the prior art, in which a dispersion containing already polymerized thiophene and a polyanion as counterion, such as the prior art PEDOT / PSS dispersion (PEDOT = poly(3,4-ethylenedioxythiophene, PSS = polystyrene sulfonate), is applied to the oxide layer, and the dispersant is then removed by evaporation. Such a method for preparing solid electrolytic capacitors is disclosed, for example, in DE 10 2005 043 828 A.

[0005] However, PEDOT / PSS dispersions are characterized by the drawback of containing a significant amount of PSS as a non-conductive inactive material. Furthermore, the presence of PSS can result in PEDOT / PSS particles in the dispersion that are too large to ensure penetration into the smaller pores of porous metal electrodes. Finally, the maximum solids content of PEDOT / PSS dispersions is often limited to values of approximately 3 wt%. To overcome these drawbacks, liquid compositions containing PEDOT derivatives that do not feature the drawbacks of known PEDOT / PSS dispersions have been prepared. Polythiophenes functionalized with sulfonate groups were first developed. The sulfonate groups allow these polythiophenes to self-dope and do not require counterions such as PSS.

[0006] For example, European Patent No. 1122274 (A1) and U.S. Patent No. 9781905 (B2) describe functionalized π-conjugated polymers such as poly(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonic acid) or poly(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-2-butanesulfonic acid) (in the scientific literature, both polymers are referred to as "PEDOT-S" or "S"). discloses the preparation of EDOT-PEDOT (referred to as "EDOT-S") by oxidative polymerization of the corresponding monomers 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonic acid and 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-2-butanesulfonic acid (EDOT-S) (both monomers are referred to as "EDOT-S" or "S-EDOT" in the scientific literature). These monomers are typically prepared by sulfonating thieno[3,4-b]-1,4-dioxin-2-methanol ("EDOT-MeOH") or a mixture of EDOT-MeOH and 3,4-(2-hydroxypropylenedioxy)-thiophene ("ProDOT-MeOH") with 1,4-butanesultone (for 1-butanesulfonic acid derivatives) or 2,4-butanesultone (for 2-butanesulfonic acid derivatives), respectively.

[0007] However, the conductivity of the conductive layers prepared with the polymer solutions obtained by these approaches still needs improvement, especially when these polymer solutions are used for the preparation of solid electrolyte layers in, for example, solid electrolytic capacitors.

[0008] It was therefore an object of the present invention to overcome the drawbacks of the prior art in the field of π-conjugated polymers.

[0009] In particular, it was an object of the present invention to provide polymer compositions comprising π-conjugated conductive polymers, preferably compositions comprising water-soluble or water-dispersible π-conjugated conductive polymers, even more preferably PEDOT-S-compositions, which are characterized in that conductive layers prepared with these polymer compositions exhibit increased conductivity compared to corresponding compositions known from the prior art.

[0010] A contribution to solving at least one of the above-mentioned objects is provided by the subject matter of the independent claims which form a category, and the dependent claims which depend therefrom represent preferred embodiments of the invention, the subject matter of which likewise contributes to solving at least one of the above-mentioned objects.

[0011] |1a| A contribution to solving at least one of the objects according to the invention is made by a first embodiment of a composition comprising at least one functionalized thiophene monomer having structure I,

[0012] [ka] During the ceremony, X 1 and X 2 represent, independently of one another, O or S, preferably O; X 3 is R 1 represents CH2-O having a carbon atom bonded to R 1represents a trivalent organic group, preferably a saturated linear or branched trivalent hydrocarbon group; R 2 represents a divalent organic group, preferably a saturated linear or branched alkylene group; M 1 is a monovalent cation, preferably H + , NH4 + , a monovalent cation selected from the group consisting of tetraalkylamines or alkali cations, more preferably H + and Na + monovalent cations selected from the group consisting of, most preferably Na + represents; the monomer composition is essentially free of unsaturated organic sulfonic acids having structure II;

[0013] [ka] During the ceremony, R 3 represents a divalent organic group, preferably a saturated linear or branched alkylene group; M 2 is a monovalent cation, preferably H + , NH4 + , a monovalent cation selected from the group consisting of tetraalkylamines or alkali cations, more preferably H + and Na + monovalent cations selected from the group consisting of, most preferably Na + and in a given composition, M 1 and M 2 and more preferably are at least somewhat identical; Alternatively, the monomer composition comprises unsaturated organic sulfonic acids having structure II in a maximum amount such that the molar ratio of the total amount of unsaturated organic sulfonic acids having structure II to the total amount of functionalized thiophene monomers having structure I is 1:32 or less, preferably 1:52 or less, more preferably 1:82 or less, even more preferably 1:112 or less, even more preferably 1:132 or less, and most preferably 1:152 or less.

[0014] The term "essentially free" as used herein in reference to the amount of unsaturated organic sulfonic acid having structure II preferably refers to the amount of such unsaturated organic sulfonic acid present in the composition, in accordance with the methods disclosed herein. 1 It has been shown that the monomer composition according to the present invention contains an unsaturated organic sulfonic acid having structure II in an amount below the detection limit when the composition is analyzed by H NMR. In a particularly preferred embodiment of the composition according to the present invention, the monomer composition does not contain an unsaturated organic sulfonic acid having structure II.

[0015] It has been observed that EDOT-S monomers known from the prior art, prepared by reacting EDOT-MeOH or a mixture of EDOT-MeOH and ProDOT-MeOH with a sultone, such as 1,4-butanesultone, contain a specific amount of unsaturated organic sulfonic acid having structure II. Surprisingly, it has also been observed that conductive layers prepared using functionalized π-conjugated polythiophenes obtained by polymerizing thiophene monomers containing a specific amount of such unsaturated organic sulfonic acid exhibit significantly lower conductivity than conductive layers prepared using functionalized π-conjugated polythiophenes obtained by polymerizing thiophene monomers containing less than a specific maximum amount of such unsaturated organic sulfonic acid. Thus, the unsaturated organic sulfonic acid appears to interfere with polymerization.

[0016] |2a| In a preferred embodiment of the monomer composition according to the present invention, the monomer composition comprises a functionalized thiophene monomer having structure Ia or structure Ib, or a mixture of functionalized thiophene monomers having structure Ia or Ib,

[0017] [ka] In formulae Ia and Ib: -m is 2 and R 3 is -CH3 and M 1 is preferably Na + Is it; or -m is 3 and R 3 is H and M 1 is preferably Na + is.

[0018] Thus, the functionalized thiophene monomer is preferably sodium 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonate or sodium 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate. In this context, it is also preferred that the unsaturated organic sulfonic acid having structure II is sodium 3-butene-1-sulfonate (in the case of sodium 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonate) or sodium 3-butene-2-sulfonate (in the case of sodium 4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate). This preferred embodiment is a second embodiment of the monomer composition according to the invention, which is preferably subordinate to the first embodiment.

[0019] |3a| In a further preferred embodiment of the monomer composition according to the invention, in formulae Ia and Ib, m is 3 and R 3 is H and M 1 is preferably Na + Thus, according to this preferred embodiment, the at least one functionalized thiophene monomer is sodium 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonate, and the monomer composition may also comprise a mixture of EDOT-S and ProDOT-S as functionalized thiophene monomers. In this regard, the unsaturated organic sulfonic acid having structure II is sodium 3-butene-1-sulfonate (i.e., R 3 is —CH—CH—. This preferred embodiment is a third embodiment of the monomer composition according to the invention, which is preferably dependent on the first or second embodiment.

[0020] |4a| In a further preferred embodiment of the monomer composition according to the invention, the at least one functionalized thiophene monomer is a mixture of functionalized thiophene monomers having structure Ia or Ib, and the weight ratio of monomers having structure Ia to monomers having structure Ib in the monomer composition (i.e., the weight ratio of EDOT-S to ProDOT-S) is at least 4:1, preferably at least 6:1, more preferably at least 8:1, even more preferably at least 10:1, even more preferably at least 25:1, even more preferably at least 50:1, and most preferably at least 100:1. This preferred embodiment is a fourth embodiment of the monomer composition according to the invention, and is preferably subordinate to the second or third embodiment.

[0021] |5a| In a further preferred embodiment of the monomer composition according to the invention, the monomer composition comprises functionalized thiophene monomers having structure I in a total amount of at least 90 wt.%, preferably at least 92.5 wt.%, even more preferably at least 95 wt.%, even more preferably at least 96 wt.%, even more preferably at least 97 wt.%, even more preferably at least 98 wt.%, even more preferably at least 99 wt.%, even more preferably at least 99.5 wt.%, and most preferably at least 99.9 wt.%, in each case based on the total weight of the monomer composition. This preferred embodiment is a fifth embodiment of the monomer composition according to the invention, which preferably depends from any one of the first to fourth embodiments.

[0022] |6a| In a further preferred embodiment of the monomer composition according to the invention, the monomer composition satisfies at least one of the following properties i) and ii), preferably both of these properties: i) the monomer composition has a color value b determined in accordance with ASTM E 308-13 of less than 0.75, preferably less than 0.70, more preferably less than 0.65 *wherein the color value is determined in transmittance using an aqueous solution containing at least one functionalized thiophene monomer having structure I in a total amount of 1 wt. % in a 0.5 mm quartz glass cuvette; ii) the monomer composition has a transmittance determined for light having a wavelength of 350 nm of at least 90%, preferably at least 91%, more preferably at least 93%, even more preferably at least 94%, even more preferably at least 95%, more preferably at least 96%.

[0023] This preferred embodiment is a sixth embodiment of the monomer composition according to the invention, which is preferably dependent on the fifth embodiment.

[0024] The monomer composition according to the present invention, preferably according to the fifth or sixth embodiment thereof, can be prepared by a method comprising the following process steps: A) providing a liquid composition comprising a thiophene alkoxy precursor monomer having structure III:

[0025] [ka] During the ceremony, X 1 and X 2 represent, independently of one another, O or S, preferably O; X 4 is R 1 CH2-O with a carbon atom bonded to - or O - represents; R 1 represents a trivalent organic group, preferably a saturated linear or branched trivalent hydrocarbon group; B) reacting a thiophene alkoxy precursor monomer having structure III with a sultone having structure IV,

[0026] [ka] 1. A process step of obtaining a reaction mixture comprising at least one functionalized thiophene monomer having structure I, wherein R 2 represents a divalent organic group, preferably a saturated, linear or branched alkylene group; C) separating the functionalized thiophene monomer having structure I in solid form from the reaction mixture; D) dissolving or dispersing the purified thiophene monomer obtained in process step C) in water to obtain an aqueous solution or dispersion, preferably an aqueous solution, which comprises the functionalized thiophene monomer having structure I in an amount of preferably at least 20% by weight, more preferably at least 30% by weight, even more preferably at least 40% by weight, most preferably at least 50% by weight, in each case based on the total weight of the aqueous solution or dispersion; E) C1-C5 alcohols, preferably alcohols selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, iso-butanol, ter-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2,2-dimethyl-1-propanol or a mixture of at least two of these alcohols, more preferably ethanol and 1-bunatol providing an alcohol selected from the group consisting of, optionally cooling the alcohol to a temperature below -10°C, preferably below -15°C, even more preferably below -20°C, and adding the aqueous solution or dispersion comprising the functionalized thiophene monomer having structure I obtained in process step D to the alcohol to obtain an alcohol solution or dispersion, which may in particular be cooled to a temperature below -10°C, preferably below -15°C, even more preferably below -20°C, in particular if the alcohol has not been cooled beforehand, thereby obtaining a precipitate comprising the purified thiophene monomer having structure I; F) A process step in which the precipitate is separated from the alcoholic solution or dispersion obtained in process step G) to obtain the monomer composition according to the invention.

[0027] In the above disclosed method, the monomer composition obtained in process step F) can be further purified by a method comprising the following process steps: G) dissolving or dispersing the purified thiophene monomer obtained in process step F) in water to obtain an aqueous solution or dispersion, preferably an aqueous solution, comprising functionalized thiophene monomer having structure I, wherein the aqueous solution or dispersion preferably comprises at least 20% by weight of functionalized thiophene monomer having structure I, more preferably at least 30% by weight, even more preferably at least 40% by weight, most preferably at least 50% by weight, in each case based on the total weight of the aqueous solution or dispersion; H) a process step of cooling the aqueous solution or dispersion obtained in process step G to a temperature below 15°C, preferably below 13°C, most preferably below 10°C, thereby re-precipitating the functionalized thiophene monomer having structure I; I) A process step of separating the precipitate from the aqueous solution or dispersion to obtain the monomer composition according to the invention.

[0028] |1b| A contribution to solving at least one of the objects according to the invention is also made by a first embodiment of a method 1 for the preparation of a polymer composition comprising a functionalized π-conjugated polythiophene, the method comprising the following process steps: I) a process step of dissolving or dispersing a monomer composition according to the present invention, preferably a monomer composition according to any one of the first to sixth embodiments thereof, in a solvent or dispersion medium, preferably water, to obtain a solution or dispersion of a functionalized thiophene monomer; II) oxidatively polymerizing a functionalized thiophene monomer having structure I in the solution or dispersion provided in process step I) to obtain a polymer composition in the form of a solution or dispersion comprising a functionalized π-conjugated polythiophene comprising repeat units having structure I′,

[0029] [ka] In the formula, the asterisk ( * ) indicates a bond to an adjacent repeat unit, and X 1 , X 2 , X 3 , R 1 , R 2 and M 1 is as defined for the functionalized thiophene monomer in the monomer composition according to the present invention; III) Optionally, a process step in which the solution or dispersion comprising the functionalized π-conjugated polythiophene obtained in process step II) is purified, preferably by ionic filtration. IV) Optionally, a process step of diluting the solution or dispersion comprising the functionalized π-conjugated polythiophene obtained in process step II) or process step III), preferably diluting the solution or dispersion with water.

[0030] |2b| In a further preferred embodiment of method 1 according to the invention, the solution or dispersion provided in process step I) comprises functionalized thiophene monomers having structure I in an amount in the range of 1 to 50% by weight, preferably in the range of 5 to 40% by weight, most preferably in the range of 10 to 30% by weight, in each case based on the total weight of the solution or dispersion provided in process step I). This preferred embodiment is a second embodiment of method 1 according to the invention, which is preferably subordinate to the first embodiment.

[0031] |3b| In a further preferred embodiment of the method 1 according to the invention, the solution or dispersion provided in process step I) further comprises at least one oxidizing agent. This preferred embodiment is a third embodiment of the method 1 according to the invention, which is preferably subordinate to the first or second embodiment.

[0032] |4b| In a further preferred embodiment of method 1 according to the invention, the solution or dispersion provided in process step I) is an aqueous solution or dispersion, and the pH of the aqueous solution or dispersion provided in process step I) is adjusted to a value below 2.5, preferably below 2.0, more preferably below 1.5, using an organic or inorganic acid, preferably selected from the group consisting of formic acid, acetic acid, lactic acid, propionic acid, citric acid, malic acid, fumaric acid, sulfuric acid, sulfonic acid, nitric acid, phosphonic acid, phosphoric acid, or a mixture of at least two of these acids, the use of sulfuric acid being particularly preferred. This preferred embodiment is a fourth embodiment of method 1 according to the invention, which is preferably subordinate to any one of the first to third embodiments.

[0033] |5b| In a further preferred embodiment of the method 1 according to the invention, the oxidative polymerization in process step II) is carried out under an inert gas atmosphere of nitrogen, argon, carbon dioxide or a mixture thereof. This preferred embodiment is a fifth embodiment of the method 1 according to the invention, which is preferably subordinate to the first to fourth embodiments.

[0034] In a further preferred embodiment of the method 1 according to the invention, the oxidative polymerization in process step II) is carried out under a pressure equal to or greater than the vapor pressure of the aqueous solution or dispersion during the polymerization reaction in process step II). This preferred embodiment is the sixth embodiment of the method 1 according to the invention, which preferably depends from any one of the first to fifth embodiments.

[0035] |7b| In a further preferred embodiment of the method 1 according to the invention, the oxidative polymerization in process step II) is carried out under reduced pressure of 0.8 bar or less. This preferred embodiment is the seventh embodiment of the method 1 according to the invention, which preferably depends from any one of the first to sixth embodiments.

[0036] In a further preferred embodiment of the method 1 according to the invention, purification in process step III) is achieved by filtration and / or by treatment with an ion exchanger. This preferred embodiment is an eighth embodiment of the method 1 according to the invention, which is preferably dependent on any one of the first to seventh embodiments.

[0037] |9b| In a further preferred embodiment of the method 1 according to the invention, the dilution in process step IV) is carried out to such an extent that the solids content of the polymer composition is in the range of 0.1 to 25% by weight, preferably in the range of 0.25 to 10% by weight, more preferably in the range of 0.5 to 5% by weight, in each case based on the total weight of the polymer composition. This preferred embodiment is a 9th embodiment of the method 1 according to the invention, which preferably depends from any one of the 1st to 8th embodiments.

[0038] |1c| A contribution to solving at least one of the objects according to the invention is also made by a first embodiment of a polymer composition 1 comprising a functionalized π-conjugated polythiophene obtainable by a method 1 according to the invention, preferably by a method 1 according to any one of the first to ninth embodiments. Preferably, the functionalized π-conjugated polythiophene obtainable by method 1 is dissolved or dispersed in water as a solvent or dispersion medium.

[0039] |1d| A contribution to solving at least one of the objects according to the invention is also made by a first embodiment of a polymer composition 2 comprising a functionalized π-conjugated polythiophene comprising repeating units having structure I′,

[0040] [ka] During the ceremony, X 1 and X 2 represent, independently of one another, O or S, preferably O; X 3 is R 1 represents CH2-O having a carbon atom bonded to R 1 represents a trivalent organic group, preferably a saturated linear or branched trivalent hydrocarbon group; R 2 represents a divalent organic group, preferably a saturated linear or branched alkylene group; M 1 is a monovalent cation, preferably H + , NH4 + , a monovalent cation selected from the group consisting of tetraalkylamines or alkali cations, more preferably H + and Na + monovalent cations selected from the group consisting of, most preferably Na + represents; In the formula, the asterisk ( * ) indicates a bond to an adjacent repeat unit; The functionalized π-conjugated polythiophene is essentially free of repeat units having structure II′;

[0041] [ka] During the ceremony, R 3 represents a divalent organic group, preferably a saturated linear or branched alkylene group; M 2 is a monovalent cation, preferably H + , NH4 + , a monovalent cation selected from the group consisting of tetraalkylamines or alkali cations, more preferably H + and Na + monovalent cations selected from the group consisting of, most preferably Na + and in a given functionalized π-conjugated polythiophene, M 1 and M2 and more preferably are at least somewhat identical; In the formula, the asterisk ( * ) indicates a bond to an adjacent repeat unit; Alternatively, the functionalized π-conjugated polythiophene comprises repeat units having structure II' in a maximum amount such that the molar ratio of the total amount of repeat units having structure II' to the total amount of repeat units having structure I' is 1:32 or less, preferably 1:52 or less, more preferably 1:82 or less, even more preferably 1:112 or less, even more preferably 1:132 or less, and most preferably 1:152 or less.

[0042] The term "essentially free" as used herein in reference to the amount of repeat units having structure II' preferably means that such repeat units are free of any repeat units that are produced in accordance with the methods disclosed herein. 1 This shows that the functionalized π-conjugated polythiophene contained in polymer composition 2 according to the present invention contains a repeat unit having structure II′ in an amount below the detection limit when the composition is analyzed by H NMR. In a particularly preferred embodiment of the composition according to the present invention, the functionalized π-conjugated polythiophene does not contain a repeat unit having structure II′.

[0043] Furthermore, as used herein, the term "polymer composition 2" preferably refers to any composition comprising a functionalized π-conjugated polythiophene comprising repeat units having structure I', regardless of its aggregation state. Thus, polymer composition 2 may be, for example, a dispersion or solution in which the functionalized π-conjugated polythiophene is dissolved or dispersed in a solvent or dispersion medium, or a conductive layer formed by applying such a solution or dispersion onto a substrate and subsequently removing the solvent or dispersion medium.

[0044] |2d| In a preferred embodiment of the polymer composition 2 according to the present invention, the functionalized π-conjugated polythiophene comprises a repeating unit having structure Ia′ or structure Ib′, or comprises a mixture of repeating units having structure Ia′ or Ib′,

[0045] [ka] In formulae Ia' and Ib': -m is 2 and R 3 is -CH3 and M 1 is preferably Na + Is it; or -m is 3 and R 3 is H and M 1 is preferably Na + is.

[0046] Thus, the functionalized π-conjugated polythiophene is preferably sodium poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonate or sodium poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate). In this context, the residues R 3 is also preferably a -CH-CH- group (in the case of sodium poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-1-sulfonate) or a -CHCH- group (in the case of sodium poly(4-[(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methoxy]butane-2-sulfonate). This preferred embodiment is a second embodiment of the polymer composition 2 according to the invention, which is preferably subordinate to the first embodiment.

[0047] |3d| In a further preferred embodiment of the polymer composition 2 according to the invention, in formulae Ia′ and Ib′, m is 3 and R 3 is H and M 1 is preferably Na +Thus, according to this preferred embodiment, the functionalized π-conjugated polythiophene is sodium poly(4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonate), and the functionalized π-conjugated polythiophene can also comprise a mixture of EDOT-S and ProDOT-S as repeat units. In this regard, the residues R in the repeat units having structure II′ are 3 is also preferably a -CH2-CH2- group. This preferred embodiment is a third embodiment of the polymer composition 2 according to the invention, which is preferably subordinate to the first or second embodiment.

[0048] |4d| In a further preferred embodiment of polymer composition 2 according to the present invention, the functionalized π-conjugated polythiophene comprises a mixture of repeat units having structure Ia' or Ib', and the weight ratio of repeat units having structure Ia' to repeat units having structure Ib' in the functionalized π-conjugated polythiophene is at least 4:1, preferably at least 6:1, more preferably at least 8:1, even more preferably at least 10:1, even more preferably at least 25:1, even more preferably at least 50:1, and most preferably at least 100:1. This preferred embodiment is a fourth embodiment of polymer composition 2 according to the present invention, and is preferably subordinate to the second or third embodiment.

[0049] |5d| In a further preferred embodiment of polymer composition 2 according to the present invention, the polymer composition is a liquid polymer composition further comprising at least one solvent or dispersion medium. The liquid polymer composition preferably comprises 0.1 to 25 wt. % of the functionalized π-conjugated polythiophene, in each case based on the total weight of the liquid polymer composition, more preferably 0.25 to 10 wt. %, and most preferably 0.5 to 5 wt. %. The solvent or dispersion medium is preferably selected from the group consisting of water, aliphatic alcohols such as methanol, ethanol, isopropanol, and butanol, diacetone alcohol, ethylene glycol, and glycerol, aliphatic ketones such as acetone and methyl ethyl ketone, aliphatic nitrites such as acetonitrile, glycol ethers such as polyethylene glycol methyl ether, and mixtures of at least two of these solvents, in particular mixtures of water and water-miscible solvents, with water being the most preferred solvent. Such liquid polymer compositions can be obtained, for example, by method 1 according to the present invention and are preferably aqueous solutions or dispersions. This preferred embodiment is a fifth embodiment of the polymer composition 2 according to the present invention, and preferably depends from any one of the first to fourth embodiments.

[0050] In a further preferred embodiment of the polymer composition 2 according to the present invention, the polymer composition comprises further additives, preferably selected from the group consisting of surface-active substances, adhesion promoters, additives that increase the conductivity, organic binders or a mixture of at least two of these further additives. This preferred embodiment is the sixth embodiment of the polymer composition 2 according to the present invention, which is preferably dependent on any one of the first to fifth embodiments, more preferably dependent on the fifth embodiment.

[0051] |7d| In a further preferred embodiment of the polymer composition 2 according to the invention, the functionalized π-conjugated polythiophene is present in the form of particles, the particle size distribution of these particles being: i) a range of 1 to 100 nm, preferably a range of 1 to 80 nm, more preferably a range of 1 to 60 nm, and most preferably a range of 5 to 40 nm;50 value (weight average particle size), and ii) 3.5 × d 50 Less than 3 × d 50 less than 2 × d 50 Less than d 90 It is characterized by value.

[0052] This preferred embodiment is the seventh embodiment of the polymer composition 2 according to the invention, and is preferably dependent on the fifth or sixth embodiment.

[0053] |8d| In a further preferred embodiment of the polymer composition 2 according to the present invention, the functionalized π-conjugated polythiophene has a weight average molecular weight M of at least 6, preferably at least 8, more preferably at least 10, more preferably at least 12, more preferably at least 14, more preferably at least 16, more preferably at least 18, more preferably at least 20. w and the molar average molecular weight M n Ratio to (M w / M n This preferred embodiment is the eighth embodiment of the polymer composition 2 according to the present invention, and preferably depends from any one of the fifth to seventh embodiments.

[0054] |9d| In a further preferred embodiment of the polymer composition 2 according to the invention, the polymer composition is a conductive layer, which comprises the functionalized π-conjugated polythiophene in an amount ranging from 50 to 99.9 wt. %, preferably from 60 to 99.5 wt. %, and most preferably from 70 to 99 wt. %, in each case based on the total weight of the conductive layer. Such a polymer composition can be obtained, for example, by the method 2 according to the invention described below. This preferred embodiment is a ninth embodiment of the polymer composition 2 according to the invention, which preferably depends on any one of the first to fourth embodiments.

[0055] In a further preferred embodiment of the polymer composition 2 according to the invention, the conductive layer made from the polymer composition has a conductivity of at least 250 S / cm, preferably at least 350 S / cm, more preferably at least 450 S / cm. This preferred embodiment is a tenth embodiment of the polymer composition 2 according to the invention, which is preferably subordinate to the ninth embodiment.

[0056] |1e| A contribution to solving at least one of the objects according to the invention is also made by a first embodiment of a method 2 for preparing a laminate, the method comprising the following process steps: A) process steps to provide a substrate; B) a process step of applying the polymer composition 1 or 2 according to the present invention, preferably the polymer composition 2 according to any one of the fifth to eighth embodiments thereof, to at least a part of at least one surface of a substrate; C) Optionally, a process step of at least partially removing the solvent or carrier medium to form a conductive layer covering at least a portion of at least one surface of the substrate.

[0057] |2e| In a preferred embodiment of the method 2 according to the invention, the substrate is an electrode body of an electrode material, and the dielectric at least partially covers one surface of this electrode material in the formation of an anode body. This preferred embodiment is a second embodiment of the method 2 according to the invention, which is preferably subordinate to the first embodiment.

[0058] |1f|A contribution to solving at least one of the objects according to the invention is also made by a laminate which can be obtained by the method 2 according to the invention, preferably by the method 2 according to the first or second embodiment.

[0059] |1g|A contribution to solving at least one of the objects according to the present invention is also made by the use of a monomer composition according to the present invention or a polymer composition 1 or a polymer composition 2 according to the present invention, preferably a polymer composition 2 according to any of the fifth to eighth embodiments thereof, for the preparation of a conductive layer in an electronic device.

[0060] In a preferred embodiment of the use according to the invention, the electronic device is selected from the group consisting of OLEDs, coated textiles, photoconductive cells, photoresistors, photoswitches, phototransistors, phototubes, IR detectors, photovoltaic devices, solar cells, coating materials for memory storage devices, field effect resistive devices, antistatic films, biosensors, electrochromic devices, solid electrolytic capacitors, energy storage devices, touch panels and electromagnetic shields. This preferred embodiment is a second embodiment of the use according to the invention and is preferably dependent on the first embodiment.

[0061] In a further preferred embodiment of the use according to the invention, the conductive layer is a solid electrolyte layer in a polymer electrolytic capacitor or a hybrid electrolytic capacitor. This preferred embodiment is a third embodiment of the use according to the invention, preferably dependent on the first or second embodiment.

[0062] Method 1 according to the present invention A contribution to solving at least one of the objects according to the present invention is made by a method 1 for the preparation of a polymer composition comprising a functionalized π-conjugated polythiophene, the method comprising the following process steps: I) a process step of dissolving or dispersing a monomer composition according to the present invention, preferably a monomer composition according to any one of the first to sixth embodiments thereof, in a solvent or dispersion medium, preferably water, to obtain a solution or dispersion of a functionalized thiophene monomer; II) oxidatively polymerizing a functionalized thiophene monomer having structure I in the solution or dispersion provided in process step I) to obtain a polymer composition in the form of a solution or dispersion comprising a functionalized π-conjugated polythiophene comprising repeat units having structure I′,

[0063] [ka] In the formula, the asterisk ( *) indicates a bond to an adjacent repeat unit, and X 1 , X 2 , X 3 , R 1 , R 2 and M 1 is as defined for the functionalized thiophene monomer in the monomer composition according to the present invention; III) Optionally, a process step in which the solution or dispersion comprising the functionalized π-conjugated polythiophene obtained in process step II) is purified, preferably by ionic filtration. IV) Optionally, a process step of diluting the solution or dispersion comprising the functionalized π-conjugated polythiophene obtained in process step II) or process step III), preferably diluting the solution or dispersion with water.

[0064] The oxidation reaction carried out in process step II) can be catalyzed by chemical oxidants, by electrochemical oxidation or by a combination of both methods. In the case of electrochemical oxidation, the electrode acts as the oxidant.

[0065] Suitable oxidizing agents for use as chemical oxidizing agents include salts of heavy metals, preferably iron salts, more preferably FeCl3, and iron(III) salts of aromatic and aliphatic sulfonic acids, HO, KCrO, peroxodisulfate salts, such as KSO, NaSO, KMnO, alkali metal perborates, and alkali metal or ammonium persulfates, or mixtures of these oxidizing substances. Heavy metal salts, peroxodisulfate salts, or mixtures thereof are particularly preferred. Further suitable oxidizing substances are described, for example, in Handbook of Conducting Polymers (Ed. Skotheim, TA), Marcel Dekker: New York, 1986, Vol. 1, pages 46-57. Particularly preferred oxidizing agents b) are peroxodisulfate salts, in particular K2S2O8, Na2S2O8, iron salts, in particular iron(III) chloride, or mixtures of peroxodisulfate salts with at least one further compound that catalyzes the cleavage of peroxodisulfate, for example mixtures of peroxodisulfate salts with iron salts. According to a particularly preferred embodiment of the process according to the invention, the oxidizing agent is a mixture of Fe2(SO4)3 and Na2S2O8.

[0066] Suitable solvents or dispersion media that can be used in Method 1 according to the present invention are those selected from the group consisting of water, water-miscible solvents, in particular aliphatic alcohols such as methanol, ethanol, isopropanol, and butanol, diacetone alcohol, ethylene glycol, and glycerol, aliphatic ketones such as acetone and methyl ethyl ketone, aliphatic nitrites such as acetonitrile, glycol ethers such as polyethylene glycol methyl ether, or mixtures of at least two of these solvents, in particular mixtures of water and water-miscible solvents. However, the most preferred solvent or dispersion medium is water. Thus, in the case of 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-1-butanesulfonic acid or 4-(2,3-dihydrothieno[3,4-b][1,4]dioxin-2-ylmethoxy)-2-butanesulfonic acid as the thiophene monomer, Method 1 according to the present invention allows the preparation of an aqueous solution or dispersion containing a functionalized π-conjugated polythiophene.

[0067] The concentration of functionalized thiophene monomers in the solution or dispersion provided in process step I) is preferably in the range of 1 to 50% by weight, preferably in the range of 5 to 40% by weight, more preferably in the range of 10 to 30% by weight, in each case based on the total weight of the solution or dispersion.

[0068] There are various ways to prepare the solution or dispersion provided in process step I). The functionalized thiophene monomer may be dissolved or dispersed in a solvent or dispersion medium, followed by the addition of the oxidizing agent (which may also be dissolved or dispersed separately in the solvent or dispersion medium), or the oxidizing agent may be dissolved or dispersed in a solvent or dispersion medium first, followed by the addition of the functionalized thiophene monomer (which may also be dissolved or dispersed separately in the solvent or dispersion medium). When using two or more oxidizing agents, such as a mixture of Fe2(SO4)3 and Na2S2O8, it is further possible to first mix one of these components with the functionalized thiophene monomer and the solvent or dispersion medium, and finally add the second oxidizing agent.

[0069] The polymerization reaction in process step II) is preferably carried out at a temperature in the range of -20°C to 200°C, preferably in the range of 0°C to 100°C, for preferably 1 to 48 hours, more preferably 5 to 20 hours.

[0070] After the polymerization reaction is complete, the solution or dispersion comprising the functionalized π-conjugated polymer, preferably the aqueous solution comprising the functionalized π-conjugated polymer, can be further purified, for example by filtration, in particular by ultrafiltration, and / or by treatment with ion exchangers, in particular anion and cation exchangers, in a further process step III).It is also possible to add further additives, as described below in connection with method 1 according to the invention.

[0071] Furthermore, the solution or dispersion comprising the functionalized π-conjugated polymer, preferably an aqueous solution comprising the functionalized π-conjugated polymer, obtained in process step II) and / or obtained after purification in process step III) may be further diluted in a further process step IV), preferably with one of the solvents or dispersion media mentioned above in connection with process step II), more preferably with water. By such a dilution step, the solids content of the solution or dispersion is preferably adjusted to a range of 0.1 to 25% by weight, preferably in the range of 0.25 to 10% by weight, more preferably in the range of 0.5 to 5% by weight, in each case based on the total weight of the solution or dispersion.

[0072] Furthermore, since the functionalized π-conjugated polythiophene obtained after polymerization in process step II) is usually present in the form of particles, the particle size distribution of the functionalized π-conjugated polythiophene in the solution or dispersion obtained in process step II) or the particle size distribution of the functionalized π-conjugated polythiophene obtained in process step III) or process step IV) after further purification and / or dilution is preferably determined by the energy input of preferably 10 to 1000 watts per liter (W / l), more preferably 20 to 500 W / l, and the ultrasonic frequency (ultrasonic vibration frequency) is preferably It can be prepared by treating the solution or dispersion with ultrasound, at 20 to 200 kHz; by treating the solution or dispersion with high pressure homogenization, where pressures of more than 100 bar, preferably more than 500 bar, and most preferably more than 1500 bar are preferably applied multiple times; or by treating the solution or dispersion with heat, where the heat treatment preferably comprises treating the solution or dispersion at a temperature in the range of 40 to 100°C, preferably in the range of 50 to 95°C, for a period of 5 minutes to 100 hours, preferably 1 to 10 hours, more preferably 2 to 8 hours.

[0073] According to a particularly preferred embodiment of the method 1 according to the invention, it is also advantageous that the solution or dispersion provided in process step I) has an oxygen content of less than 1,000 ppm, preferably less than 500 ppm, more preferably less than 100 ppm, more preferably less than 10 ppm, more preferably less than 1 ppm, more preferably less than 0.5 ppm and most preferably less than 0.25 ppm, in each case based on the total weight of the solution or dispersion. According to a particularly preferred embodiment of the method 1 according to the invention, the solution or dispersion provided in process step I) is completely free of oxygen (i.e. the oxygen content is 0 ppm).

[0074] There are different approaches to adjust the oxygen content in the solution or dispersion provided in process step I) and to maintain this low oxygen content during the polymerization reaction in process step II).

[0075] According to one approach, the solution or dispersion provided in process step I) (or the liquid components used to prepare the solution or dispersion) can be degassed, for example by introducing an inert gas such as N, argon, CO or mixtures thereof, into the solution or dispersion provided in process step I) to reduce the initial oxygen content in the solution or dispersion. Alternatively, the solution or dispersion provided in process step I) (or the liquid components used to prepare the solution or dispersion) can be subjected to treatment with reduced pressure, for example by stirring the solution or dispersion while applying a vacuum, or to treatment with ultrasound, or to a combination of treatment with reduced pressure and treatment with ultrasound, in order to reduce the initial oxygen content.

[0076] To ensure that a low oxygen content is maintained during the polymerization reaction in process step II), it may be advantageous to carry out the polymerization reaction under an inert gas atmosphere, preferably under N, CO, argon or a mixture of at least two of these inert gases; it may also be advantageous to carry out the oxidative polymerization in process step II) under a pressure equal to or greater than the vapor pressure of the solution or dispersion during the polymerization reaction in process step II). Preferably, the oxidative polymerization in process step II) is carried out under a pressure that is at least 0.1 mbar, more preferably at least 0.5 mbar, and most preferably at least 1 mbar higher than the vapor pressure of the solution or dispersion during the polymerization reaction in process step II). To ensure that a low oxygen content is maintained during the polymerization reaction in process step II), it is also possible to carry out the oxidative polymerization in process step II) under reduced pressure, preferably at a pressure of 0.8 bar or less, most preferably at a pressure of 0.5 bar or less.

[0077] Method 2 according to the present invention A contribution to the achievement of the above-mentioned object is also made by a method 2 for the preparation of a laminate, which method comprises the following process steps: A) process steps to provide a substrate; B) a process step of applying the liquid polymer composition 1 or the liquid polymer composition 2 according to the present invention, preferably the liquid polymer composition 2 according to any one of the fifth to eighth embodiments thereof, to at least a part of at least one surface of a substrate; C) Optionally, a process step of at least partially removing the solvent to form a conductive layer covering at least a portion of at least one surface of the substrate.

[0078] According to a particularly preferred embodiment of the method 2 according to the invention, the substrate is an electrode body of an electrode material, and the dielectric at least partially covers one surface of this electrode material under the formation of an anode body. Thus, in such an embodiment, the process steps A) and B) comprise: A) a process step of providing an electrode body of an electrode material, wherein a dielectric material at least partially covers one surface of the electrode material under formation of an anode body; B) A process step of introducing the liquid polymer composition 1 or 2 according to the present invention, preferably the liquid polymer composition 2 according to any one of the fifth to eighth embodiments thereof, into at least a part of the electrode body.

[0079] In process step A), an electrode body of electrode material (a dielectric at least partially covers one surface of this electrode material to form the anode body) is first provided.

[0080] In principle, the electrode body can be produced by pressing a high-surface-area valve metal powder and sintering it to obtain a porous electrode body. Preferably, an electrical contact wire of a valve metal, such as tantalum, is also conventionally pressed into the electrode body. The electrode body is then coated with a dielectric, i.e., oxide layer, for example, by electrochemical oxidation. Alternatively, to obtain an anode foil with a porous region, a metal foil can be etched and coated with a dielectric by electrochemical oxidation. In a wound capacitor, the anode foil and cathode foil with a porous region that form the electrode body are separated by a separator and wound together.

[0081] In the context of the present invention, a valve metal should be understood to mean a metal whose oxide layer does not allow current to flow equally in both directions. When a voltage is applied to the anode, the oxide layer of the valve metal blocks the current, while when a voltage is applied to the cathode, a large amount of current is generated, which may destroy the oxide layer. Valve metals include Be, Mg, Al, Ge, Si, Sn, Sb, Bi, Ti, Zr, Hf, V, Nb, Ta, and W, as well as alloys or compounds of at least one of these metals with other elements. The most well-known representative examples of valve metals are Al, Ta, and Nb. Compounds with electrical properties equivalent to valve metals have metallic conductivity, can be oxidized, and their oxide layers have the above-mentioned properties. For example, NbO has metallic conductivity, but is generally not considered a valve metal. However, since an oxidized NbO layer has typical properties of a valve metal oxide layer, NbO or alloys or compounds of NbO with other elements are typical examples of compounds with electrical properties equivalent to valve metals. Tantalum, aluminum electrode materials and electrode materials based on niobium or niobium oxide are preferred. Tantalum and aluminum are very particularly preferred as electrode materials.

[0082] To produce an electrode body, which often has porous regions, the valve metal can be sintered, for example, in powder form, to obtain a typically porous electrode body, or the porous structure can be imprinted onto the metal body, the latter being done, for example, by etching a foil.

[0083] For convenience, a body having a porous region will also be referred to as porous hereinafter. Thus, for example, an electrode body having a porous region will also be referred to as a porous electrode body. On the other hand, a porous body may have multiple channels extending throughout it and thus be sponge-like. This is often the case when tantalum is used to construct a capacitor. Furthermore, it is possible for only the surface to have pores, with the region below the surface pores being a solid structure. This situation is often observed when aluminum is used to construct a capacitor. Preferably, the electrode body is porous.

[0084] The electrode body thus produced, often porous, is then oxidized to form a dielectric by applying a voltage in a suitable electrolyte, such as, for example, aqueous phosphoric acid or ammonium adipate. The level of this formation voltage varies depending on the thickness of the oxide layer to be achieved or the subsequent operating voltage of the capacitor. Preferred formation voltages are in the range of 1 to 1000 V, particularly preferably in the range of 2 to 500 V, and very particularly preferably in the range of 1 to 300 V. According to a first specific embodiment of the method for producing a capacitor, the formation voltage is in the range of 1 to 20 V, and according to a second specific embodiment of the method for producing a capacitor, the formation voltage is in the range of 30 to 100 V.

[0085] The porous electrode bodies used as a rule preferably have a porosity of 10 to 90%, preferably 30 to 80%, particularly preferably 50 to 80% and an average pore diameter of 10 to 10,000 nm, preferably 20 to 5,000 nm, particularly preferably 50 to 3,000 nm.

[0086] According to a specific embodiment of Method 2 of the present invention, the electrolytic capacitor produced is an aluminum-wound capacitor. In this case, a porous aluminum foil is formed as the electrode material, and an aluminum oxide coating is formed as the dielectric. The aluminum foil thus obtained (anode foil) is then provided with contact wires and wound with a further, optionally porous, aluminum foil (cathode foil) also provided with contact wires, the two foils being separated from each other by one or more separators, for example, based on cellulose or preferably synthetic paper. After winding, the anode body thus obtained is fixed, for example, with adhesive tape. The separator can be carbonized by heating in an oven. The method and manner of producing the anode body for this aluminum-wound capacitor are well known in the prior art and are described, for example, in U.S. Pat. No. 7,497,879 (B2).

[0087] According to a further particular embodiment of method 2 according to the invention, the electrolytic capacitors produced are aluminum stack capacitors or tantalum electrolytic capacitors ("tantalum elco"), in particular tantalum electrolytic capacitors with a polymer outer layer such as those described in DE 10 2009 007 594 (A).

[0088] In process step B) of method 2 according to the present invention, polymer composition 1 or 2 according to the present invention, preferably polymer composition 2 according to any of its fifth to eighth embodiments, is applied to at least a portion of the anode body. In this connection, it should be noted that before applying polymer composition 1 or 2 to at least a portion of the anode body, other compositions for forming an electrically conductive layer, such as a PEDOT / PSS dispersion, may be applied to the anode body. It is therefore not necessarily necessary to apply polymer composition 1 or 2 directly to at least a portion of the dielectric layer of the anode body.

[0089] Polymer composition 1 or 2, preferably polymer composition 2 according to any one of the fifth to eighth embodiments thereof, is introduced into the porous region by known methods, such as impregnation, dipping, pouring, dripping, spraying, atomizing, knife coating, brushing, or printing, such as inkjet, screen, or tampon printing. Preferably, introduction is carried out by immersing the anode body in the polymer composition, thereby impregnating the anode body with the polymer composition. Immersion in or impregnation with the polymer composition is preferably carried out for a time period ranging from 1 second to 120 minutes, particularly preferably from 5 seconds to 60 minutes, and most preferably from 10 seconds to 15 minutes. Introduction of the polymer composition into the anode body can be facilitated, for example, by increasing or decreasing pressure, vibration, ultrasound, or heat.

[0090] The polymer composition 2 according to any one of its fifth to eighth embodiments, preferably used in process step B), comprises, besides the residue of the functionalized π-conjugated polymer, the solvent or dispersion and, optionally, the oxidizing agent in reduced form, further additives, such as surface-active substances, for example anionic surfactants, such as alkylbenzenesulfonic acids and salts, paraffin sulfonates, alcohol sulfonates, ether sulfonates, sulfosuccinates, phosphate esters, alkyl ether carboxylic acids or carboxylates, cationic surfactants, such as quaternary alkylammonium salts, nonionic surfactants, such as linear alcohol ethoxylates, oxoalcohol ethoxylates, alkylphenol ethoxylates or alkylpolyglucosides, in particular Dyn surfactants, commercially available under the trademarks Zonyl® and Zonyl®, or adhesion promoters, such as organofunctional silanes or their hydrolysates, for example 3-glycidoxypropyltrialkoxysilane, 3-amino-propyl-triethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane or octyltriethoxysilane, crosslinkers, for example melamine compounds, masked isocyanates, functional silanes, for example tetraethoxysilane, alkoxysilane hydrolysates, for example those based on tetraethoxysilane, epoxy silanes, for example 3-glycidoxypropyltrialkoxysilane, polyurethane, polyacrylate or polyolefin dispersions.

[0091] Preferably, the polymer composition 2 according to any one of the fifth to eighth embodiments thereof, used in process step B), may optionally contain further additives that increase the electrical conductivity, such as compounds containing ether groups, such as tetrahydrofuran, compounds containing lactone groups, such as γ-butyrolactone, γ-valerolactone, compounds containing amide or lactam groups, such as caprolactam, N-methylcaprolactam, N,N-dimethylacetamide, N-methylacetamide, N,N-dimethylformamide (DMF), N-methylformamide. amido, N-methylformanilide, N-methylpyrrolidone (NMP), N-octylpyrrolidone, pyrrolidone, etc.; sulfones and sulfoxides, for example, sulfolane (tetramethylene sulfone), dimethyl sulfoxide (DMSO), etc.; sugars or sugar derivatives, for example, sucrose, glucose, fructose, lactose, etc.; sugar alcohols, for example, sorbitol, mannitol, etc.; furan derivatives, for example, 2-furancarboxylic acid, 3-furancarboxylic acid, etc.; glycerol, diglycerol, triglycerol, or tetraglycerol.

[0092] The polymer composition 2 according to any one of its fifth to eighth embodiments, preferably used in process step B), may further comprise, as further additives, one or more organic binders soluble in water or water-miscible solvents. Furthermore, the polymer composition 2 may also comprise, as further additives, one or more compounds that improve the thermal stability of the conductive layer, such as aromatic compounds having at least two OH groups, such as gallic acid (3,4,5-trihydroxybenzoic acid), tannins or flavonoids.

[0093] Preferably, the viscosity of the polymer composition 2 according to any one of its fifth to eighth embodiments, used in process step B), is between 0.01 and 1,000 mPa×s (at 20°C and 100°C), depending on the application method. -1(measured with a rheometer at a shear rate of 100 Hz). Preferably, the viscosity is 1 to 500 mPa×s, particularly preferably 1 to 250 mPa×s. In the case of the production of aluminum wound capacitors, the viscosity is very particularly preferably in the range of 1 to 200 mPa×s, while in the case of the production of tantalum electrolytic capacitors or aluminum stacked capacitors, the viscosity is very particularly preferably in the range of 1 to 50 mPa×s. Viscosity adjustment can be achieved, for example, by adding suitable rheology modifiers as further additives.

[0094] The solids content of the polymer composition 2 according to any one of its fifth to eighth embodiments, preferably used in process step B), is preferably in the range of 0.01 to 20% by weight, particularly preferably in the range of 0.1 to 15% by weight, most preferably in the range of 0.25 to 10% by weight, in each case based on the total weight of the liquid polymer composition. The solids content of the liquid polymer composition is determined by drying the liquid polymer composition at a temperature high enough to remove the solvent or dispersion medium.

[0095] According to a particularly preferred embodiment of method 2 according to the invention, the polymer composition 2 according to any one of its fifth to eighth embodiments, which is introduced into the capacitor body, comprises not only a functionalized π-conjugated polymer but also (in addition to this self-doped conductive polymer) a hetero-doped conductive polymer, preferably PEDOT / PSS as disclosed in WO 2014 / 048562 A2. The disclosure of WO 2014 / 048562 A2 regarding the combined use of a self-doped polymer such as PEDOT-S with a hetero-doped polymer such as PEDOT / PSS for the formation of a solid electrolyte is incorporated herein by reference and forms part of the disclosure of the present application.

[0096] After impregnation of the anode body with the polymer composition 2 according to any one of the fifth to eighth embodiments thereof as described above, it is advantageous to at least partially remove the solvent or dispersion medium contained in the polymer composition in a subsequent process step C), thereby forming a solid electrolyte which completely or partially covers the dielectric and thus the capacitor body. In this connection, the coverage of the dielectric with the solid electrolyte is preferably at least 10%, particularly preferably at least 25%, most preferably at least 50%, which coverage can be measured by measuring the capacitance of the capacitor in the dry and humid state at 120 Hz, as described in DE 10 2005 043 828 (A).

[0097] The removal or curing is preferably carried out by removing the solvent from the polymer composition and drying, the drying being preferably carried out at temperatures in the range from 20°C to 260°C, particularly preferably in the range from 50°C to 220°C, most preferably in the range from 80°C to 200°C. Of course, it is also possible to at least partially remove the solvent or dispersion medium by freeze-drying. Process steps B) and C) can also be repeated once or in this manner several times in succession in order to adapt the thickness of the layer of solid electrolyte deposited on the dielectric or the filling degree of the electrolyte in the electrode body to specific requirements.

[0098] After the capacitor bodies are produced in this way, they can be further modified by methods and manners known to those skilled in the art. In the case of tantalum electrolytic capacitors, the capacitor body can be covered with a polymer outer layer, for example, as described in German Patent Application Publication No. 102004022674(A) or German Patent Application Publication No. 102009007594(A), and / or with a graphite layer and a silver layer as known from German Patent Application Publication No. 102005043828(A). In the case of aluminum-wound capacitors according to the teachings of U.S. Pat. No. 7,497,879(B2), the capacitor body is assembled into an aluminum beaker with a sealing glass and mechanically tightly closed by crimping. The capacitor can then be aged to eliminate defects in the dielectric in a known manner. [Brief explanation of the drawings]

[0099] The invention will now be explained in more detail using non-limiting figures and examples.

[0100] [Figure 1] 1 shows the correlation between the conductivity of a conductive layer prepared with a PEDOT-S composition according to the present invention and the content of sodium 3-butene-1-sulfonate in the EDOT-S monomer solution from which the PEDOT-S was prepared. [Figure 2] Figure 1 shows the H NMR spectrum (DO) of sodium 3-butene-1-sulfonate (Butene-S Na). [Figure 3] Figure 1 shows a comparison of the H NMR spectra (DO) of butene-S Na (top) and butene-S Na enriched EDOT-S Na monomer product mixture (bottom).

[0101] Test Method UV / VIS spectroscopy (transmission) and color value b * Measurement of Color value b * was determined according to ASTM E 308-13.

[0102] Prior to measurement, a 1 wt% solution of a given functionalized thiophene monomer was prepared in fully deionized water to ensure a fully solubilized solution. Transmission spectra were acquired using a Perkin Elmer Lambda900 UV / VIS / NIR spectrometer with a resolution of 5 nm per data point. The lamp was operated for 30 min before measurement.

[0103] All spectra were generated using a quartz glass cuvette (0.5 mm). A background transmission spectrum (200-2500 nm) was measured with fully deionized water to generate a baseline spectrum. A 1% solution was then measured. After generating the transmission spectrum, the color value b was calculated using WinCol software by selecting the standard illuminant D65 and a 10° observer.* It was decided that:

[0104] 1 Determination of the content of unsaturated organic sulfonic acids by H NMR The content of unsaturated organic sulfonic acid, particularly the content of sodium 3-butene-1-sulfonate, in the composition of functionalized thiophene monomers is 1 The characteristic peaks were determined by H NMR via the presence of characteristic peaks. Table 1 shows these characteristic peaks for 3-butene-1-sulfonate (butene-S Na).

[0105] [Table 1]

[0106] [ka]

[0107] The integrals of the EDOT-S Na and ProDOT-S Na aromatic thiophene protons (6.53 and 6.74 ppm, respectively) and the integral of the terminal alkene proton (1) allowed the determination of the respective ternary molar ratios (EDOT-S Na, ProDOT-S Na, and butene-S Na).

[0108] conductivity A cleaned glass substrate measuring 50 mm x 50 mm was placed on a spin coater, and 10 ml of the liquid composition according to the present invention was distributed over the substrate. The excess solution was then shaken off by rotating the plate. The coated substrate was then dried on a hot plate at 130°C for 15 minutes. The layer thickness was then measured using a layer thickness measuring device (Tencor, Alphastep 500). The electrical conductivity was measured by depositing a 25 mm long Ag electrode at a distance of 10 mm through a shadow mask. To obtain the specific electrical resistivity, the surface resistance measured with an electrometer (Keithly 614) was multiplied by the layer thickness. The electrical conductivity is the reciprocal of the specific electrical resistivity.

[0109] average Unless otherwise stated, the average corresponds to the arithmetic mean value.

[0110] Solids The solids content was determined gravimetrically using a precision scale (Mettler AE240). First, the empty weighing bottle, including the lid, was weighed (Weight A). Then, 3 g of the dispersion to be analyzed was filled into the bottle, the lid was closed, and the bottle was reweighed to determine the exact total weight (Weight B). The bottle was placed in a drying oven (Memmert UNB200) at 100 °C for 16 h with ventilation. Because the dried dispersion material is hygroscopic, it is important to immediately cover the sample bottle with a glass lid when removing it from the oven. After a 10-15 minute cooling period, the bottle, including the lid, was reweighed to determine Weight C. At least two further repetitions were always performed to allow for the determination of the average solids content. [Example]

[0111] Example 1: Synthesis of EDOT-MeOH / ProDOT-MeOH (not of the present invention) EDOT-MeOH is a precursor compound to EDOT-S Na and was prepared in a multi-step synthesis from dimethyl 3,4-dihydroxythiophene-2,5-dicarboxylate according to Chevrot et al. (J. Electroanal. Chem. 1998, 443, 217-226). The synthesis proceeds in three steps:

[0112] Process 1 Dimethyl 3,4-dihydroxythiophene-2,5-dicarboxylate (14.0 g, 54 mmol) was dissolved in ethanol (270 mL) and heated to reflux. Then, under reflux, a solution of epibromohydrin (6 mL, 70 mmol) and potassium carbonate (1.5 g, 11 mmol) in distilled water (80 mL) was added to the reaction solution. The mixture was refluxed for 1 hour, and then additional amounts of epibromohydrin (10.4 g, 122 mmol) and potassium carbonate (0.8 g, 6 mmol) were added. The reaction was refluxed for an additional 72 hours. The resulting solution was extracted twice with chloroform (200 mL). The organic layer was then washed with a 5% aqueous solution of potassium chloride (200 mL). The organic phase was dried over MgSO4, and the solvent was removed under vacuum by rotary evaporation. A yellow solid was obtained, which was recrystallized from diethyl ether (100 ml) to give a white crystalline powder (Intermediate 1, 78% yield). Intermediate 1 was obtained with a 6-membered ring (EDOT):7-membered ring (ProDOT) ratio of approximately 90:10, respectively.

[0113] Intermediate 1: Thieno[3,4-b]-1,4-dioxine-5,7-dicarboxylic acid, 2,3-dihydro-2-(hydroxymethyl)-5,7-dimethyl ester and isomers.

[0114] Process 2 Intermediate 1 from step 1 (11.54 g, 36 mmol) was added to a solution of potassium hydroxide (12 g, 214 mmol) in distilled water (250 mL). After the reactants were completely dissolved, the solution was heated to reflux for a total of 2 h. The volume of the solution was then reduced to 100 mL by rotary evaporation. Concentrated HCl (24 mL) was slowly added to the cooled solution (ice bath) with continuous stirring. After 2 h, the white precipitate was isolated by filtration and dried under vacuum at 80 °C to give solid Intermediate 2 as a light gray powder (9.22 g, 35 mmol, 97%).

[0115] Intermediate 2: 2,3-Dihydro-2-(hydroxymethyl)thieno[3,4-b]-1,4-dioxine-5,7-dicarboxylic acid and isomers.

[0116] Process 3 Intermediate 2 from step 2 (9.22 g, 35 mmol) was mixed with copper chromite catalyst (1 g, 3.2 mmol) and freshly distilled quinoline (50 mL). The suspension was refluxed under nitrogen at 180 °C for 2 h. After cooling, diethyl ether was added, and the insoluble precipitate was removed by filtration. The filtrate was then washed with 5% HCl and 5% potassium chloride solution. The organic phase was dried over MgSO4, filtered, and the filtrate was concentrated by rotary evaporation. The resulting residue was purified by column chromatography (diethyl ether:cyclohexane (95:5)) to give 2,3-dihydrothieno[3,4-b][1,4]dioxin-2-yl)methanol (EDOT-MeOH) (3.22 g, 19 mmol, 54%).

[0117] The final EDOT-MeOH:ProDOT-MeOH ratio was obtained at a ratio of approximately 90:10 ( 1 1 H NMR).

[0118] Example 2: Synthesis of EDOT-S Na / ProDOT-S Na containing alkenes (not of the present invention) For the preparation of EDOT-S Na monomers with sulfonic acid side chains, the product of Example 1, EDOT-MeOH, was reacted in an additional step according to Chevrot et al. (J. Electroanal. Chem. 1998, 443, 217-226).

[0119] Sodium hydride (0.38 g, 16 mmol, 60% oil dispersion) was added to dry toluene (50 mL) and placed under a nitrogen atmosphere with continuous stirring. EDOT-MeOH (2.24 g, 13 mmol) prepared in Example 1 dissolved in toluene (20 mL) was added slowly with vigorous stirring. The reaction mixture was heated to reflux for 1 hour. 1,4-butanesultone (1.8 g, 13 mmol) dissolved in 15 mL of toluene was then added dropwise slowly to the stirred solution. The reaction was refluxed for an additional 2 hours and stirred at room temperature for 17 hours. Acetone (200 mL) was added with vigorous stirring. The resulting suspension was filtered through a fritted filter and washed with additional acetone under a nitrogen atmosphere. The product was dried under vacuum at 40 °C to give "Sample #1" as an orange / off-white powder (3.7 g, 11.2 mmol, 86%).

[0120] In Example 2, the resulting product mixture ratio of EDOT-S Na:ProDOT-S Na:Butene-S Na (=sodium 3-butene-1-sulfonate) was about 77.9:16.7:5.4 ( 1 1 H NMR).

[0121] Example 3: Purification of EDOT-S Na A (present invention) The product mixture (30 g) obtained in Example 2 was dissolved in distilled water (30 g) at 80°C for up to 1 hour, or until a 50% by weight solution was obtained. The solution was filtered to remove undissolved solids. The solution was cooled to room temperature. EtOH (100 mL) was cooled externally with dry ice (-40°C) and stirred while the EDOT-S Na solution was added dropwise over 30 minutes and stirred for an additional hour after addition. The resulting suspension was filtered through a fritted filter, and the yellow solid was dried in a vacuum cupboard (50°C) for at least 3 days to obtain "Sample #2" (recovered mass = 93%).

[0122] EDOT-S Na with reduced alkene content was obtained at an EDOT-S Na:ProDOT-S Na:butene-S Na molar ratio of approximately 80:17:3 ( 1 1 H NMR).

[0123] Example 4: Purification of EDOT-S Na B (present invention) The product mixture (50 g) obtained in Example 2 was dissolved in distilled water (50 g) at 80°C for up to 1 hour, or until a 50% by weight solution was obtained. The solution was filtered to remove undissolved solids. The solution was cooled to room temperature. EtOH (350 mL) was cooled externally with dry ice (-20°C) and stirred while the EDOT-S Na solution was added dropwise over 2-3 hours, followed by stirring for an additional hour. The resulting suspension was filtered through a fritted filter, and the yellow solid was dried in a vacuum cupboard (50°C) for at least 3 days to obtain "Sample #3" (recovered mass = 68%).

[0124] EDOT-S Na with reduced alkene content was obtained at an EDOT-S Na:ProDOT-S Na:butene-S Na molar ratio of approximately 84:15:1.2 ( 1 1 H NMR).

[0125] Example 5: Purification of EDOT-S Na C (present invention) The product mixture (5 g) obtained in Example 2 was dissolved in distilled water (20 g) at 80°C for 1 hour, or until a 20% by weight solution was obtained. The solution was filtered to remove undissolved solids. The solution was cooled to room temperature. nBuOH (2500 mL) was cooled externally with dry ice (-40°C) and stirred while the EDOT-S Na solution was added dropwise over 30 minutes and stirred for an additional hour after addition. The resulting suspension was filtered through a fritted filter, and the yellow solid was dried in a vacuum cupboard (50°C) for at least 3 days to obtain "Sample #4" (recovered mass = 42%).

[0126] EDOT-S Na with reduced alkene content was obtained at an EDOT-S Na:ProDOT-S Na:butene-S Na molar ratio of approximately 99:0.5:0.75 ( 1 1 H NMR).

[0127] Example 6: Purification of EDOT-S Na D (present invention) The product mixture (20 g) obtained in Example 4 was dissolved in distilled water (30 mL) at 80° C. for 1 hour, or until a 40% by weight dark orange solution was obtained, which was then allowed to cool slowly to room temperature. The solution was then cooled to 9° C. using a thermostatically controlled cooling system for approximately 48 hours, at which time a precipitate was observed. Filtration through a fritted filter, followed by drying in a vacuum cupboard (50° C.) for at least 3 days, afforded a pale yellow solid as "Sample #5" (recovered mass=58%).

[0128] For purification steps B and D, EDOT-S Na was obtained in an EDOT-S Na:ProDOT-S Na:Butene-S Na molar ratio of about 98.5:1.5:0 ( 1 1 H NMR) was obtained (total mass recovery=39%).

[0129] Example 7: Polymerization of the product mixture formed in Example 2 (not of the invention) The product mixture obtained in Example 2 (5.00 g) was dissolved in distilled water (25 mL) and degassed with nitrogen for 60 minutes while cooling to 10°C. Iron(III) sulfate (0.8 g, 2 mmol) was dissolved in distilled water (5 mL) and degassed with nitrogen for 30 minutes. The iron(III) sulfate solution was then added all at once to the EDOT-S Na solution. DMSO (30 mg, 0.38 mmol) was then also added to the solution. Sodium persulfate (3.98 g, 16.7 mmol) was added to distilled water (10 mL) and degassed with nitrogen for 60 minutes. The reaction solution was stirred throughout, and the temperature was maintained at 10°C throughout the slow addition of the sodium persulfate solution. The reaction was allowed to warm to room temperature for 17 hours, after which the solution was added to ion exchangers (Lewatit® S108H and Lewatit® MP 62) and the mixture was stirred at room temperature for 30 minutes. This process was repeated three times, filtering each time. After filtering off the ion exchanger, the solution was diluted to 0.87% solids. Subsequent ultrasonic treatment yielded a dark blue polymer solution.

[0130] Example 8: Polymerization of the product mixture formed in Example 3 (invention) The product mixture obtained in Example 3 (5.00 g) was polymerized according to the protocol outlined in Example 7 to give a dark blue polymer solution with a solids content of 1.10%.

[0131] Example 9: Polymerization of the product mixture formed in Example 4 (invention) The product mixture from Example 4 (5.00 g) was polymerized according to the protocol outlined in Example 7 to give a dark blue polymer solution with a solids content of 1.07%.

[0132] Example 10: Polymerization of the product mixture formed in Example 5 (Invention) The product mixture from Example 5 (5.00 g) was polymerized according to the protocol outlined in Example 7 to give a dark blue polymer solution with a solids content of 1.16%.

[0133] Example 11: Polymerization of the product mixture formed in Example 6 (invention) The product mixture from Example 6 (5.00 g) was polymerized according to the protocol outlined in Example 7 to give a dark blue polymer solution with 1.2% solids.

[0134] Table 2 shows the purity ratios (EDOT-S Na:ProDOT-S Na:Butene-S Na) and color values b for the product mixtures prepared according to Examples 2-6. * Table 3 shows the conductivity and % solids of the resulting polymer films for each corresponding polymer dispersion produced according to Examples 7-11.

[0135] [Table 2]

[0136] [Table 3]

[0137] Figure 1 shows the relationship between the conductivity of a given thin film and the alkene content of the original EDOT-S Na monomer product mixture. This graph demonstrates that a lower % alkene content is required to achieve higher conductivity in the final thin film.

Claims

1. Structure I 【Chemical 1】 (In the formula, X １ and X ２ are each independently O or S, X ３ is R １ CH having a carbon atom bonded to ２ represents —O or represents O, R １ represents a trivalent organic group, R ２ represents a divalent organic group, M １ represents a monovalent cation), The monomer composition comprises a monomer having Structure II 【Chemistry 2】 (In the formula, R ３ represents a divalent organic group, M ２ represents a monovalent cation), or or said monomer composition comprising said unsaturated organic sulfonic acid having structure II in a maximum amount such that the molar ratio of the total amount of said unsaturated organic sulfonic acid having structure II to the total amount of functionalized thiophene monomers having structure I is 1:32 or less.

2. The monomer composition comprises a functionalized thiophene monomer having structure Ia or structure Ib, or a mixture of functionalized thiophene monomers having structure Ia or Ib. 【Chemistry 3】 wherein in formulas Ia and Ib: -m is 2 and R ３ Ha-CH ３ Or or -m is 3 and R ３ is H), the monomer composition of claim 1.

3. In formulas Ia and Ib, m is 3 and R ３ The monomer composition of claim 2 wherein is H.

4. 4. The monomer composition of any one of claims 1 to 3, wherein the monomer composition comprises functionalized thiophene monomers having structure I in a total amount of at least 90% by weight, based on the total weight of the monomer composition.

5. The following characteristics: i) the monomer composition has a color value b determined in accordance with ASTM E 308-13 of less than 0.75 ＊ wherein the color value b is determined in transmittance using an aqueous solution containing at least one functionalized thiophene monomer having structure I in a total amount of 1 wt. % in a 0.5 mm quartz glass cuvette. ＊ having ii) the monomer composition has a transmittance determined for light having a wavelength of 350 nm of at least 90%; The monomer composition according to claim 4, which satisfies at least one of the following conditions:

6. 1. A method for preparing a polymer composition comprising a functionalized π-conjugated polythiophene, comprising: I) a process step of dissolving or dispersing the monomer composition according to any one of claims 1 to 5 in a solvent or dispersion medium to obtain a solution or dispersion of the functionalized thiophene monomer; II) oxidatively polymerizing the functionalized thiophene monomer having structure I in the solution or dispersion provided in process step I) to obtain a polymer composition in the form of a solution or dispersion comprising a functionalized π-conjugated polythiophene comprising repeat units having structure I′, 【Chemistry 4】 In the formula, an asterisk ( ＊ and a process step of obtaining a polymer composition wherein the repeat units each represent a bond to adjacent repeat units.

7. Structure I' 【Chemistry 5】 (In the formula, X １ and X ２ are each independently O or S, X ３ is R １ CH having a carbon atom bonded to ２ represents —O or represents O, R １ represents a trivalent organic group, R ２ represents a divalent organic group, M １ represents a monovalent cation), In the formula, an asterisk ( ＊ ) represents a bond to an adjacent repeating unit; The functionalized π-conjugated polythiophene has the structure II' 【Chemistry 6】 (In the formula, R ３ represents a divalent organic group, M ２ represents a monovalent cation) or (wherein the asterisk ( ＊ ) indicates a bond to an adjacent repeating unit, Or a polymer composition, wherein the functionalized π-conjugated polythiophene comprises repeat units having structure II' in a maximum amount such that the molar ratio of the total amount of repeat units having structure II' to the total amount of repeat units having structure I' is 1:32 or less.

8. The functionalized π-conjugated polythiophene comprises a repeat unit having structure Ia′ or structure Ib′, or comprises a mixture of repeat units having structure Ia′ or Ib′. 【Chemistry 7】 (In formulas Ia' and Ib', m is 2, and R ３ Ha-CH ３ Or or m is 3, and R ３ is H), the polymer composition of claim 7.

9. In formulas Ia′ and Ib′, m is 3 and R ３ 9. The polymer composition of claim 7 or 8, wherein is H.

10. 10. The polymer composition of any one of claims 7 to 9, wherein the polymer composition is a liquid polymer composition further comprising at least one solvent or dispersion medium, and the liquid polymer composition comprises the functionalized π-conjugated polythiophene in an amount ranging from 0.1 to 25 wt%, based on the total weight of the liquid polymer composition.

11. 10. The polymer composition of claim 7, wherein the polymer composition is a conductive layer, and the conductive layer comprises the functionalized π-conjugated polythiophene in an amount ranging from 50 to 99.9 wt %, based on the total weight of the conductive layer.

12. 1. A method for the preparation of a laminate, comprising: A) a process step of providing a substrate; B) applying the polymer composition of claim 10 to at least a portion of at least one surface of the substrate; C) optionally a process step of at least partially removing said solvent or carrier medium to form a conductive layer covering at least a portion of at least one surface of said substrate.

13. 13. The method of claim 12, wherein the substrate is an electrode body of an electrode material, and a dielectric material at least partially covers one surface of the electrode material under formation of an anode body.

14. Use of the monomer composition according to any one of claims 1 to 5 or the polymer composition according to any one of claims 7 to 11 for the preparation of a conductive layer in an electronic device.

15. 15. The use according to claim 14, wherein the electronic device is selected from an OLED, a coated fiber, a photoconductive cell, a photoresistor, a photoswitch, a phototransistor, a phototube, an IR detector, a photovoltaic device, a solar cell, a coating material for a memory storage device, a field effect resistive device, an antistatic film, a biosensor, an electrochromic device, a solid electrolytic capacitor, an energy storage device, a touch panel, and an electromagnetic shield.

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