EP2190934A1 - Particles having a core-shell structure for conductive layers - Google Patents
Particles having a core-shell structure for conductive layersInfo
- Publication number
- EP2190934A1 EP2190934A1 EP08787555A EP08787555A EP2190934A1 EP 2190934 A1 EP2190934 A1 EP 2190934A1 EP 08787555 A EP08787555 A EP 08787555A EP 08787555 A EP08787555 A EP 08787555A EP 2190934 A1 EP2190934 A1 EP 2190934A1
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- European Patent Office
- Prior art keywords
- optionally substituted
- particles
- conductive
- dispersions
- particles according
- Prior art date
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3081—Treatment with organo-silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/3072—Treatment with macro-molecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
- C09C1/30—Silicic acid
- C09C1/309—Combinations of treatments provided for in groups C09C1/3009 - C09C1/3081
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
-
- 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
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2993—Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
- Y10T428/2991—Coated
- Y10T428/2998—Coated including synthetic resin or polymer
Definitions
- the present invention relates to particles with a Kera-cup structure containing an acid-functionalized core based on an inorganic material and a shell containing at least one conductive polythiophene, dispersions containing such particles and their preparation and use.
- water-insoluble or poorly soluble conductive polymers e.g. Polyaniline, polypyrrole or polythiophene can be dispersed by the presence, dissolved or dispersed counterions.
- TEOS tetraethylorthosilicate
- EDT 3,4-ethylenedioxythiophene
- SiO 2 dispersion (Langmuir, 2003, 19, 4523), EDT is polymerized with ammonium persulfate as the oxidant in the presence of p-toiol sulfonic acid. During the polymerization, a precipitate forms, which was washed by redispersing and centrifuging and processed to a pressure. At this pressure of the material, a conductivity of 0.2 S / cm was measured.
- Toluene sulfonic acid is not described in detail; it is merely referred to that p-toluenesulfonic acid acts to protonate EDT and as a counterion, so that it can not be assumed that only catalytic amounts of p-Toulolsulfonklare were used. A description of the conductivity of the particles produced is missing in this publication.
- the object underlying the present invention was therefore to provide such particles and dispersions containing these particles. Another object was to find a simple process for their preparation.
- the present invention thus relates to particles having a core-shell structure, wherein the core is based on an inorganic material and the shell contains at least one conductive polythiophene, characterized in that the core based on an inorganic material contains covalently bound acid groups.
- Suitable inorganic materials for the core are, in particular, metal oxides. These are preferably one or more oxide (s) of silicon, aluminum, titanium or zirconium. Particularly preferred is Si ⁇ iciumdioxid.
- the particles according to the invention can preferably be prepared by first functionalizing dispersed inorganic particles - hereinafter also referred to as inorganic primary particles - with the acid groups and then applying the shell containing the conductive polythiophene (s).
- the inorganic material is therefore preferably present in dispersed form as starting material.
- Aqueous silica dispersions have been known for a long time. Depending on the manufacturing process, they are available in different forms.
- Silica dispersions suitable according to the invention may be those based on silica sol, silica gel, pyrogenic silicic acids, precipitated silicas or mixtures of these.
- SiO 2 dispersions suitable for functionalization are sedimentation-stable, colloidal solutions of amorphous SiO 2 in water and / or alcohols and other polar solvents. They are mostly water-liquid, and the commercial products sometimes have high solids concentrations, preferably from 5 to 60 wt .-% SiO 2J and have a high stability against gelation.
- silica sols are milky cloudy over opalescent to colorless clear, depending on the size of the
- the particles of the silica sol have diameters of 3 nm to 250 nm, preferably 5 nm to 150 nm.
- the particles are spherical, spatially limited and preferably electrically negatively charged.
- In the interior of the individual particles is usually a skeleton of siloxane bonds, which results from the combination of [S i ⁇ , j] tetrahedra or polysilicic acids.
- SiOH groups are arranged on the surface.
- Preferred for various applications are stable silica sols with specific surface areas of about 30 to 1000 m 2 / g. The specific surface areas can be determined either by the BET method (see S. Brunauer PH Emmet and E. Teller, J. Am.
- Silica sols are unstable to Elektrolylzusatz, such as. For example, sodium chloride, ammonium chloride and potassium fluoride.
- silica usually contain monovalent cations such.
- Silica sols are produced by condensation of monosilicic acids via a nucleation phase in a so-called growth process in which small SiO 2 particles grow on the presence of germs. It is based on molecular silicate solutions, freshly prepared dilute silicic acid solutions (so-called fresh sol) containing particles ⁇ 5 nm. Less commonly, silica sol is obtained by peptization of silica gels or prepared by other methods, eg, dispersing amorphous SiO 2 particles. The vast majority of the technical scale carried out process for the preparation of silica sols uses as starting material technical water glasses.
- Natronwasserg ⁇ as has a composition of Na 2 O 3.34 SiO 2 and is preferably by melting of quartz sand with
- Soda or a mixture of sodium sulfate and carbon produced to obtain a transparent colorless glass, so-called piece glass.
- This piece glass reacts in ground form with water at elevated temperature and pressure to colloidal, strongly alkaline solutions, which are then subjected to a further purification.
- Pyrogenic silica can be prepared by flame hydrolysis or by the arc process.
- the dominant synthesis method for fumed silicas is flame hydrolysis, in which tetrachlorosilane is decomposed in an oxyhydrogen flame.
- the resulting silica is X-ray amorphous.
- Pyrogenic silicic acids have significantly less OH groups than precipitated silica on their virtually pore-free surface.
- the fumed silica prepared by flame hydrolysis usually has a specific surface area of 50 to 600 m 2 / g and a primary particle size of 5 to 50 nm, the silica produced by the arc process has a specific surface area of 25 to 300 m 2 / g and a primary particle size from 5 to 500 nm.
- SiO 2 raw material such as, for example, pyrogenic or precipitated silicic acid used, it is converted into an example aqueous SKV dispersion by dispersing.
- Dispersants of the prior art preferably those suitable for producing high shear rates, such as Ultraturrax or dissolver disks, are used to prepare the silica dispersions.
- Silica sols very particularly preferably aqueous silica sols, are particularly preferably used as the silicon dioxide dispersions. Suitable silica sols are also commercially available.
- the acid groups covalently bonded to the inorganic core directly or via alkyl chains are preferably bonded to its surface.
- strongly acidic acid groups come into question. These are preferably sulfonic acid and / or mercapto groups.
- acid groups also mean their salts, in particular alkali metal, such as sodium and potassium, alkaline earth, such as magnesium and calcium, or ammonium salts.
- B is a (p + 1) -valent bridge gear
- p is an integer from 1 to 3 and
- M is hydrogen, an alkali metal cation, in particular Li + , Na + , or K + , an alkaline earth metal cation, in particular Mg 2+ or Ca 2+ , or NH /.
- B is more preferably bivalent, ie p is 1.
- B is a linear or branched alkylene group having 1 to 15 C atoms, optionally interrupted by one or more oxygen atoms, a cycloalkylene group having 5 to 8 C atoms or a unit of the formulas
- Silica sols containing sulfonic acid groups in particular those of the formula (Z), particularly preferably those of the formula (Z-I)
- the sulfur content based on SiO 2 of the silica sol is 0.1 to 30 mol%, preferably 0.1 to 8 mol%, in particular 1 to 5 mol%.
- the sulfur content can be determined, for example, by elemental analysis.
- Suitable conductive polythiophenes in the context of the invention are preferably those comprising recurring units of the general formula (I),
- R 1 and R 2 independently of one another are each H, an optionally substituted C 1 -C 8 -alkyl radical or an optionally substituted C 1 -C 8 -alkoxy radical, or the like
- R 1 and R 2 together represent an optionally substituted Q-Cs-alkylene radical, an optionally substituted Q-Cg-alkylene radical, wherein one or more C-atoms are replaced by one or more identical or different heteroatoms selected from O or S.
- A represents an optionally substituted C r C 3 -alkylene radical, preferably an optionally substituted C 2 -C -alkylene radical,
- Y stands for O or S
- R is a linear or branched, optionally substituted Cj-Cig-alkyl radical, an optionally substituted Cs-Ci 2 -cycloalkyl radical, an optionally substituted C 6 -C 4 -aryl radical, an optionally substituted C 7 -Cig-aralkyl radical, an optionally substituted C i C 4 -hydroxyalkyl radical or a hydroxyl radical,
- x is an integer from 0 to 8, preferably 0 or 1
- radicals R are attached to A, they may be the same or different.
- the general formula (I-a) is understood to mean that x substituents R can be bonded to the alkylene radical A.
- R and x have the abovementioned meaning.
- the polythiophene having repeating units of the general formula (Ia) and / or (Ib) is a copolymer of recurring units of the formula (I-aa-1) and (I-aa-2), (I-aa 1) and (Ib), (I-aa-2) and (Ib) or (I-aa-1), (I-aa-2) and (Ib), where copolymers of recurring units of the formula (I- aa-1) and (I-aa-2) as well as (I-aa-1) and (Ib) are preferred.
- the polythiophenes may be neutral or cationic.
- polythiophenes are cationic, with “cationic” referring only to those located on the polythiophene backbone
- the polythiophenes can carry positive and negative charges in the structural unit, with the positive charges on the polythiophene backbone Polythiophenhauptkette and the negative charges optionally to the through
- the positive charges of the polythiophene main chain can be partially or completely saturated by the optionally present anionic groups on the radicals R.
- the polythiophenes in these cases can be cationic, neutral or even anionic. Nevertheless, they are all considered as cationic polythiophenes in the context of the invention, since the positive charges on the polythiophene main chain are relevant.
- the positive charges are not shown in the formulas because their exact number and position can not be determined properly. However, the number of positive charges is at least 1 and at most n, where n is the total number of all repeating units (equal or different) within the polythiophene.
- conductive polythiophenes having a specific conductivity of more than 10 '8 Sem “1 , more preferably of more than 10 " 6 Sem ' 1 , most preferably of more than 10 "4 Scm "! - Made on layers of these conductive polythiophenes in the dried state - produced.
- these counterions are preferably provided by the acid groups covalently bound to the inorganic core.
- the present invention also relates to dispersions comprising the particles according to the invention.
- the inventive particles preferably have a particle size of 5 nm to 100 microns, more preferably a particle size of 10 nm to 20 microns.
- the particle size distribution can be determined by means of ultracentrifuge (Colloid Polymer Sci. 1989, 267, 1113-1116). For particles that swell in the dispersion, the particle size is determined in the swollen state.
- a particle size distribution of the particles refers to a mass distribution of the particles in the dispersion as a function of the particle size.
- a dso value of the particle size distribution indicates that 50% of the total mass of all particles can be assigned to particles which have a size smaller than or equal to the d 5 o value.
- a d 1 value of the particle size distribution indicates that 90% of the total mass of all particles can be assigned to particles which have a size less than or equal to the d 90 value.
- the dispersions of the invention may have a pH of from 1 to 14, preferably a pH of from 1 to 8.
- the solids content of the particles according to the invention in the dispersion according to the invention is preferably 0.1 to 90% by weight, more preferably 0.5 to 30% by weight and most preferably 0.5 to 10% by weight.
- the particles according to the invention preferably form a stable dispersion.
- unstable dispersions can also be obtained. These can then be stirred, rolled or shaken, for example, before use in order to ensure a uniform distribution of the particles according to the invention.
- the preparation of the inventive particles is preferably carried out directly in dispersion.
- a further subject of the present invention is therefore a process for the preparation of the dispersions according to the invention, characterized in that dispersions containing particles based on an inorganic material, i. Dispersions containing inorganic primary particles, ⁇ siert functionally by chemical reaction with acid groups and then in the presence of these particles containing covalently bonded acid groups precursors for the preparation of conductive polythiophenes are oxidatively polymerized.
- reaction in an aqueous medium having a water content of at least 75 wt .-% in at least one of the stages a), b) 5 bl) or b2), based on the respective reaction mixture was carried out.
- SO 3 M-group-containing compound is preferably the compound of formula OI to call
- n and s each represent a number from 0 to 3
- t 1 to 15, preferably 1 to 6, in particular 3,
- R is Ci-CrAlkyl, in particular methyl or ethyl.
- M, s and q have the abovementioned meaning, in particular s stands for 3 and q for 0.
- a mercapto (SH) compound is preferably used, which is oxidized after the reaction to a SO 3 M ⁇ kau.
- Preferred mercapto compounds are those of the formula (W) (CH 3) q Si (0R) m (0H) s - (CHj) rSH (IV) 5
- t is 1 to 15, in particular 1 to 6, preferably 3 and
- R has the abovementioned meaning, preferably methyl or ethyl.
- a preferred compound of the formula (IV) is that of the formula (IVa)
- reaction of silica sol with compounds carrying functional groups, in particular with mercapto compounds, preferably those of the formulas (IV) and (FVa), is preferably characterized in that the two components at a temperature of O 0 C to
- reaction mixture 150 0 C, preferably 0 0 C to 100 0 C, react.
- possible condensation products such as water and alcohols, preferably continuously, the reaction mixture can be removed, for example by distillation.
- Oxidizing agent preferably H 2 O 2
- Oxidizing agent are oxidized in a known manner to sulfonic acid groups.
- the oxidation may alternatively be carried out with ammonium peroxodisulfate, sodium peroxodisulfate, potassium peroxodisulfate, iron nitrate, tert-butyl hydroxyperoxide, oxone (Caro's acid), potassium iodate, potassium periodate, periodic acid.
- F is a functional group which can be reacted further, e.g. an SH group, a primary or secondary amino group, and q and m have the abovementioned meaning.
- Preferred functional group-bearing compounds are:
- B 1 represents an aromatic bridge member having 6 or 10 carbon atoms, can be reacted.
- Particular preference is given to benzene disulfonyl chlorides, toluene disulfonyl chlorides or naphthalenedisulfonyl chlorides or naphthalene trisulfonyl chlorides, which in turn may be substituted again, so that, for example, a microparticle system of the general formula
- Sulfonic acid groups are substituted.
- Such compounds can be:
- the compounds III to XVII are preferably used in an amount of from 0.1 to 30 mol%, in particular from 0.5 to 5 mol%, based on the silicon content of the silica sol.
- the invention relates to the products obtainable by reaction of silica sol and a compound of the formula HI or IV and, if appropriate, subsequent oxidation.
- Sulfone group-containing silica sols are already in other forms (for example, other particle size or sulfur content) for catalyst purposes from EP-A-1 142 640, EP-A-63 471, DB-A-2 426 306 and R-D. Badley, T. Ford. J. Org. Chem. 1989, 54, 5437-5443.
- the polymerization of thiophenes requires the presence of an acid.
- the functionalization of the inorganic core by means of an acid thus has the advantage of strongly bonding the shell to the core. If this acid is merely added as an additive as in the case of Armes and Han (Langmuir, 2003, 19, 4523), then no direct link between the core and the resulting polymer is ensured.
- a complex bond of a polycation is built up to a polyanion, so that a total of one solid
- the acid-functionalized primary particles are initially introduced, preferably directly in dispersion, in preferred embodiments in the form of a silica sol.
- Suitable dispersants also referred to below as solvents, are, for example, aliphatic alcohols, aliphatic ketones, aliphatic carboxylic acid esters, aliphatic nitriles such as acetonitrile, aliphatic sulfoxides, aliphatic carboxylic acid amides, aliphatic and araliphatic ethers and water.
- Preferred solvent is water or mixtures containing water. Particularly preferred solvent is water.
- precursors for the preparation of conductive polythiophenes, one or more oxidizing agents and optionally a catalyst are added and the precursors for the production of conductive Polythiophe ⁇ en oxidatively polymerized.
- the oxidative polymerization takes place from the precursors described above, for example analogously to the conditions mentioned in EP-A 440 957.
- An improved variant for the preparation of the dispersions is the use of ion exchangers for the removal of the inorganic salt content or a part thereof. Such a variant is described for example in DE-A 19 627 071.
- the ion exchanger can for example be stirred with the product or the
- Product is conveyed through a column filled with ion exchanger.
- ion exchanger for example, low metal contents can be achieved.
- a further filtration of the dispersion can take place.
- Preferred precursors for the preparation of conductive polythiophenes are thiophenes of the general formula (H)
- R 1 and R 2 have the meaning given for the general formula (I).
- Preferred thiophenes of the general formula (II-a) are those of the general formula (II-a-1) and / or (I ⁇ -a-2)
- Derivatives of the thiophenes listed above can also be used in the context of the invention as precursors for the preparation of conductive polythiophenes.
- derivatives of the thiophenes listed above are, for example, dimers or trimers of these thiophenes.
- the derivatives can be constructed from the same or different monomer units and can be used in pure form and mixed with one another and / or with the abovementioned thiophenes.
- Oxidized or reduced forms of these thiophenes and thiophene derivatives are also included within the meaning of the invention by the term thiophenes and thiophene derivatives, provided that the same conductive polymers are formed during their polymerization as in the thiophenes and thiophene derivatives listed above.
- the thiophenes may optionally be used in the form of solutions.
- Suitable solvents which may be mentioned are, in particular, the following inert organic solvents under the reaction conditions; aliphatic alcohols such as methanol, ethanol, i-propanol and butanol; aliphatic ketones such as acetone and methyl ethyl ketone; aliphatic carboxylic acid esters such as ethyl acetate and butyl acetate; aromatic hydrocarbons such as toluene and xylo !; aliphatic hydrocarbons such as hexane, heptane and cyclohexane; Chlorinated hydrocarbons such as dichloromethane and dichloroethane; aliphatic nitriles such as acetonitrile, aliphatic sulfoxides and sulfones such as dimethylsulfoxide and sulfolane; aliphatic carboxylic acid
- Thiophenes which are liquid under the oxidation conditions, can also be polymerized in the absence of solvents.
- the oxidizing agent used may be the oxidizing agent known to those skilled in the art for the oxidative polymerization of thiophenes; these are for example in J. Am. Chem, Soc, 85, 454 (1963).
- oxidizing agents such as iron (III) salts of inorganic acids, such as FeCl 3 , Fe (ClG f ) 3 , and the iron-IH salts of organic acids and inorganic acids having organic radicals, furthermore H 2 O 2 , KaCr 2 O 7 , alkali metal and ammonium peroxodisulfates, such as sodium or potassium peroxodisulfate, alkali metal perborates, potassium permanganate, copper salts, such as copper tetrafluoroborate or cerium (FV " ) salts or CeO ⁇ .
- iron (II) salts of organic acids containing inorganic acids are the iron (III) salts of the sulfuric acid semiesters of C 1 -C 2 () -alkanols, e.g. called the Fe-HI salt of lauryl sulphate.
- iron (III) salts of organic acids there may be mentioned, for example: the Fe-DI salts of C 1 -C 20 -alkanesulfonic acids, such as methane and dodecanesulfonic acid, aliphatic C 1 -C 2 () -carboxylic acids, such as 2-ethylhexylcarboxylic acid, aliphatic Perfluorocarboxylic acids such as trifluoroacetic acid and perfluorooctanoic acid, aliphatic dicarboxylic acids such as oxalic acid and especially of aromatic, optionally substituted by C ] -C2 ( ) alkyl groups
- Sulfonic acids such as benzenesulfonic acid, p-To ⁇ uolsulfonklare and dodecylbenzenesulfonic acid and Cycloalkansuifonklaren such as camphorsulfonic acid.
- the aforementioned Fe-III salts may optionally be used as catalysts in combination with easily handled Oxsdationm ⁇ tteln such as H 2 O 2 , K 2 Cr 2 O 7 , alkali metal and Ammoniumperoxodisulfate, such as sodium or potassium peroxodisulfate, alkali metal perborates, potassium permanganate, copper salts, such as Kupferfertetrafluoroborat or cerium (IV) salts or CeO 2 can be used.
- Oxsdationm ⁇ tteln such as H 2 O 2 , K 2 Cr 2 O 7
- alkali metal and Ammoniumperoxodisulfate such as sodium or potassium peroxodisulfate
- alkali metal perborates alkali metal perborates
- potassium permanganate potassium permanganate
- copper salts such as Kupferfertetrafluoroborat or cerium (IV) salts or CeO 2
- C r C 5 ⁇ alkylene radicals A are in the context of the invention: methylene, ethylene, n-propylene, n-butylene or n-pentylene, Ci-Cg-AIkylenreste beyond n-hexylene, n-heptylene and n-octylene.
- C 1 -C 3 -alkylidene radicals are C r C 3 -alkylene radicals listed above in the context of the invention containing at least one double bond.
- Ci-C "-Oxythiaalkylenreste and Ci-Cg-Dithiaalkylenreste are in the context of the invention for the C r Cg-Dioxyalkylenreste corresponding to the above-mentioned C r Q Alkyienreste, Ci-C 8 - Oxythiaalkylenreste and C) -C r Dithiaalkylenreste.
- C r C 18 alkyl represents for the purposes of the invention are linear or branched Cj-Cjg-Aikylreste such as methyl, Bthyl, n- or iso-propyl, n-, iso-, sec- or tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, C5-Ci
- Aryl radicals such as phenyl or naphthyl, and C 7 -C 8 aralkyl C 7 -C r AraIkylreste such as benzyl, o, m ⁇ , p-tolyl, 2,3-, 2,4-, 2,5-, 2,6-, 3,4-, 3,5-xylyl or mesityl.
- Ct-C ) g - Alkoxy radicals are in the context of the invention for the alkoxy radicals corresponding to the above-mentioned C r Cig- alkyl radicals. The preceding list serves to exemplify the invention and is not to be considered as exhaustive.
- substituents of the preceding radicals are numerous organic groups, for example alkyl, cycloalkyl, aryl, halogen, ether, thioether,
- the particles of the invention 'or dispersions suitable for the production of conductive layers.
- the present invention furthermore relates to the use of the particles or dispersions according to the invention for the production of conductive layers.
- the thus obtainable conductive layers preferably have a specific conductivity of more than 10 "8 SCm" 1, more preferably of more than 10 '6 Sem "5 very particularly preferably of more than 10" 4 Sem' 'on.
- the dispersions of the invention may be prepared by known methods, e.g. by spin coating, impregnation, pouring, dripping, spraying, spraying, knife coating, brushing or printing, for example ink-jet, screen or pad printing, be applied to a suitable surface.
- conductive layers which are distinguished by a particular hardness.
- the hardness of the layers can be determined using pencil hardnesses in accordance with DIN EN 13523.
- Scratch-resistant layers with conductive, in particular antistatic properties are of interest, for example, for the surface treatment of plastics. Due to the antistatic properties, they can be used in areas where antistatic charging is to be avoided, e.g. in the case of articles of daily use made of plastic, clothing, clean room equipment and cleanroom consumables.
- the present invention furthermore relates to the conductive layers, preferably prepared using the particles or dispersions of the invention.
- the following examples serve to exemplify the invention and are not to be considered as limiting.
- Example 2 Preparation of a dispersion according to the invention containing SiOVPEDT particles according to the invention
- Solids content 2.99 wt .-% based on the total weight of the dispersion
- Example 2 10 g of the dispersion of Example 2 according to the invention were mixed with 10 g of ethanol, 1 g of dimethyl sulfoxide and 0.1 g of a surfactant.
- a cleaned glass substrate was placed on a spin coater and 10 ml of the above mixture was spread on the substrate. Subsequently, the supernatant solution was spun off by rotation of the plate. Thereafter, the thus coated substrate was dried at 200 ° C. for 5 minutes on a hot plate.
- the layer thickness was 140 nm (Tencor, Alphastep 500).
- the conductivity was determined by evaporating over a shadow mask Ag electrodes with a length of 2.5 cm at a distance of 0.5 mm.
- the surface resistance determined with an electrometer was multiplied by the layer thickness to the electrical specific
- the resistivity of the layer was 120 ohnvcm. This corresponded to a conductivity of 0.0083 S / cm.
- the hardness of the dispersion of the invention was compared with reference materials belonging to the prior art. To produce the films, the sample from Example 2 and the
- the hardness of the layers was determined by means of pencil hardnesses in accordance with DIN EN 13523. For this purpose, pencils of various hardnesses were drawn over the respective film by means of a carriage. The hardest pencil hardness that leaves no scratches on the film is the hardness of the film.
- the reference material was a poly (3,4-ethylenedioxythiophene) (PEDT):
- Table 1 shows the masses used of the respective mixtures and the hardnesses achieved thereby. It is clear that a higher hardness is achieved with the sample according to the invention from Example 2 than with the means previously available according to the prior art. Both Baytron® P and the mixture of Baytron® P and the sample from Example 1 show in combination with the binder lower hardnesses (HB or F) than the sample according to the invention from Example 2 (H). Only the pure binder (Baypret®) shows a higher hardness, but this system lacks conductive or antistatic properties.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
- Non-Insulated Conductors (AREA)
- Silicon Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE200710046904 DE102007046904A1 (en) | 2007-09-28 | 2007-09-28 | Particles with core-shell structure for conductive layers |
PCT/EP2008/061326 WO2009043648A1 (en) | 2007-09-28 | 2008-08-28 | Particles having a core-shell structure for conductive layers |
Publications (1)
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EP2190934A1 true EP2190934A1 (en) | 2010-06-02 |
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Application Number | Title | Priority Date | Filing Date |
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EP08787555A Withdrawn EP2190934A1 (en) | 2007-09-28 | 2008-08-28 | Particles having a core-shell structure for conductive layers |
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US (1) | US20100316862A1 (en) |
EP (1) | EP2190934A1 (en) |
JP (1) | JP2010541141A (en) |
KR (1) | KR20100126261A (en) |
DE (1) | DE102007046904A1 (en) |
TW (1) | TW200932853A (en) |
WO (1) | WO2009043648A1 (en) |
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JP2011116860A (en) * | 2009-12-03 | 2011-06-16 | Shin Etsu Polymer Co Ltd | Conductive coating, method for producing the same and conductive molded product |
JP2011228222A (en) * | 2010-04-23 | 2011-11-10 | Oike Ind Co Ltd | Conductive coating composition |
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US11756742B1 (en) | 2019-12-10 | 2023-09-12 | KYOCERA AVX Components Corporation | Tantalum capacitor with improved leakage current stability at high temperatures |
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DE102004049012A1 (en) * | 2004-10-05 | 2006-04-06 | Lanxess Deutschland Gmbh | Use of amino groups-, sulfonicacid-groups and mercapto groups containing layer silicate as micro particles in the paper preparation (in retention) |
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- 2007-09-28 DE DE200710046904 patent/DE102007046904A1/en not_active Withdrawn
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2008
- 2008-08-28 KR KR1020107008817A patent/KR20100126261A/en not_active Application Discontinuation
- 2008-08-28 US US12/679,809 patent/US20100316862A1/en not_active Abandoned
- 2008-08-28 WO PCT/EP2008/061326 patent/WO2009043648A1/en active Application Filing
- 2008-08-28 JP JP2010526231A patent/JP2010541141A/en active Pending
- 2008-08-28 EP EP08787555A patent/EP2190934A1/en not_active Withdrawn
- 2008-09-26 TW TW97136996A patent/TW200932853A/en unknown
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TW200932853A (en) | 2009-08-01 |
DE102007046904A1 (en) | 2009-04-09 |
US20100316862A1 (en) | 2010-12-16 |
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KR20100126261A (en) | 2010-12-01 |
JP2010541141A (en) | 2010-12-24 |
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