EP1727839A1 - Utilisation de particules a noyau et enveloppe - Google Patents

Utilisation de particules a noyau et enveloppe

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Publication number
EP1727839A1
EP1727839A1 EP04797749A EP04797749A EP1727839A1 EP 1727839 A1 EP1727839 A1 EP 1727839A1 EP 04797749 A EP04797749 A EP 04797749A EP 04797749 A EP04797749 A EP 04797749A EP 1727839 A1 EP1727839 A1 EP 1727839A1
Authority
EP
European Patent Office
Prior art keywords
core
shell
poly
matrix
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP04797749A
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German (de)
English (en)
Inventor
Holger Winkler
Götz Peter HELLMANN
Tilmann Eberhard Ruhl
Peter Spahn
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1727839A1 publication Critical patent/EP1727839A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
    • C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
    • C04B38/063—Preparing or treating the raw materials individually or as batches
    • C04B38/0635—Compounding ingredients
    • C04B38/0645—Burnable, meltable, sublimable materials
    • C04B38/067—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00

Definitions

  • the invention relates to the use of core-shell particles for the production of moldings with regularly arranged cavities, a process for the production of moldings with regularly arranged cavities and the corresponding moldings.
  • Shaped bodies with regularly arranged cavities in the sense of the present invention are materials which have three-dimensional photonic structures.
  • three-dimensional photonic structures i. a. Systems understood that have a regular, three-dimensional modulation of the dielectric constant (and therefore also the refractive index). If the periodic modulation length corresponds approximately to the wavelength of the (visible) light, the structure interacts with the light in the manner of a three-dimensional diffraction grating, which manifests itself in angle-dependent color phenomena.
  • An example of this is the naturally occurring gemstone opal, which consists of a densely packed ball packing made of silicon dioxide balls and cavities in between, which are filled with air or water.
  • Three-dimensional inverse structures can be created by template synthesis:
  • Capillary effects are filled with a gaseous or liquid precursor or a solution of a precursor.
  • Si0 2 spheres can be arranged in the densest packing, the hollow volumes are filled with solutions containing tetraethyl orthotitanate. After several tempering steps, are in an etching process
  • De La Rue et al. (De La Rue et al. Synth. Metals, 2001, 116, 469) describe the production of inverse, consisting of Ti0 2 opals according to the following method: A dispersion of 400 nm in size
  • Polystyrene balls are dried on a filter paper under an IR lamp.
  • the filter cake is suctioned off with ethanol, transferred to a glove box and infiltrated with tetraethyl orthotitanate using a water jet pump.
  • the calcination takes place in the tube furnace at 575 ° C. for 8 hours in an air stream, whereby titanium dioxide is formed from the ethoxide and the latex particles are burned out.
  • An inverse TiO 2 opal structure remains.
  • Martinelli et al. (M. Martinelli et al. Optical Mater. 2001, 17, 11) describe the production of inverse Ti0 2 opals using 780 nm and 3190 nm large polystyrene balls.
  • a regular arrangement in the densest spherical packing is achieved by centrifuging the aqueous spherical dispersion at 700-1000 rpm for 24-48 hours and then decanting, followed by air drying.
  • the regularly arranged balls are moistened with ethanol on a filter on a Buchner funnel and then dropwise provided with an ethanolic solution of tetraethyl orthotitanate.
  • the sample is dried in a vacuum desiccator for 4 to 12 hours. This filling procedure is repeated 4 to 5 times.
  • the polystyrene balls are then burned out at 600 ° C - 800 ° C for 8 - 10 hours.
  • Stein et al. (A. Stein et al. Science, 1998, 281, 538) describe the synthesis of inverse Ti0 2 opals from polystyrene spheres with a diameter of 470 nm as a template. These are made in a 28 hour process, subjected to centrifugation and air dried. Then the latices template are applied to a filter paper.
  • Ethanol is sucked into the latex template via a Büchner funnel, which is connected to a vacuum pump. Then tetraethyl orthotitanate is added dropwise with suction. After drying in a vacuum desiccator for 24 h, the latices are burned out at 575 ° C for 12 h in an air stream.
  • Vos et al. (WL Vos et al. Science, 1998, 281, 802) produce inverse Ti0 2 opals by using polystyrene spheres with diameters of 180-1460 nm as templates.
  • a sedimentation technique is used to set the densest spherical packing of the spheres, which is supported by centrifugation for up to 48 h.
  • an ethanolic solution of tetra-n-propoxy orthotitanate is added to it in a glove box. After about 1 h, the infiltrated material is brought into the air to allow the precursor to react to form Ti0 2 . This procedure is repeated eight times to ensure complete filling with Ti0 2 .
  • the material is then calcined at 450 ° C.
  • Core-shell particles the shell of which forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution, are described in German patent application DE-A-10145450.
  • the use of such core-shell particles, the shell of which forms a matrix and whose core is essentially solid and has an essentially monodisperse size distribution as a template for the production of inverse opal structures and a method for the production of inverse opal-like structures using such core-shell particles is described in the older German patent application DE 10245848.0.
  • the moldings described with regularly arranged cavities ie inverse opal structure
  • a first object of the present invention is therefore the use of core-shell particles, the shell of which forms a matrix and whose core essentially consists of a degradable polymer and has an essentially monodisperse size distribution and whose shell can be pyrolyzed to a carbon matrix , for the production of moldings with regularly arranged cavities.
  • a carbon matrix is understood to mean materials that largely correspond to those of carbon fibers.
  • the carbon matrix according to the invention is elemental carbon, preferably amorphous or semi-crystalline form, the crystalline components being present in the graphite modification or modifications similar to graphite, such as fullerenes, carbon nanotubes and similar graphite-like structures.
  • the carbon matrix is
  • Conductor polymers such as polyimides, which are used in thermal
  • the shell in the core-shell particles consists of essentially uncrosslinked organic polymers which
  • ⁇ are grafted onto the core via an at least partially cross-linked intermediate layer, the sheath preferably being formed essentially from polyacrylonitrile (PAN) or polymethacrylonitrile or copolymers which contain polyacrylonitrile or polymethacrylonitrile, such as polystyrene acrylonitrile 5 (PSAN).
  • PAN decomposes to a suitable carbon matrix at temperatures of 250-280 ° C.
  • Another object of the present invention is a process for the production of moldings with, regularly arranged cavities, 0 characterized in that core-shell particles, the shell of which forms a matrix and whose core consists essentially of a degradable polymer and an essentially monodisperse Has size distribution and the shell can be pyrolyzed to a carbon matrix 5 , processed using a mechanical force and elevated temperature to form, preferably films, and then the cores are removed by degradation and the shell decomposes at elevated temperature to a carbon matrix becomes.
  • core-shell particles the shell of which forms a matrix and whose core consists essentially of a degradable polymer and an essentially monodisperse Has size distribution and the shell can be pyrolyzed to a carbon matrix 5 , processed using a mechanical force and elevated temperature to form, preferably films, and then the cores are removed by degradation and the shell decomposes at elevated temperature to a carbon matrix becomes.
  • the degradable core in the core-shell particles is thermally degradable and consists of polymers which can either be thermally depolymerized, i.e. decompose into their monomers under the action of temperature, or the core consists of 5 polymers which decompose into low molecular weight components decay, which are different from the monomers. It is important that the core polymers are degraded at a temperature that is equal to or lower than the temperature at which the carbon matrix is formed.
  • Suitable polymers can be found, for example, in the table “Thermal
  • Suitable thermally degradable polymers are in particular
  • Poly (styrene) and derivatives such as poly ( ⁇ -methylstyrene) or poly (styrene) derivatives which carry substituents on the aromatic ring, such as, in particular, partially or perfluorinated derivatives, poly (acrylate) and poly (methacrylate) derivatives and their esters, particularly preferably poly (methyl methacrylate) or
  • Poly (cyclohexyl methacrylate) or copolymers of these polymers with other degradable polymers such as preferably styrene-ethyl acrylate copolymers or methyl methacrylate-ethyl acrylate copolymers,
  • Cellulose and derivatives such as oxidized cellulose and cellulose triacetate,
  • Polyketones e.g. Poly (methyl isopropenyl ketone) or poly (methyl vinyl ketone),
  • Polyolefins e.g. Polyethylene and polypropylene, polyisisoprene, polyolefin oxides, such as zu.B. Polyethylene oxide or polypropylene oxide, polyethylene terephthalate, polyformaldehyde, polyamides such as nylon 6 and nylon 66, polyperfluoroglucarodiamidine, polypropylene polyolefins such as
  • poly (styrene) and derivatives such as poly ( ⁇ -methylstyrene) or poly (styrene) derivatives which carry substituents on the aromatic ring, such as, in particular, partially or perfluorinated derivatives, poly (acrylate), is particularly preferred.
  • poly (methacrylate) derivatives and their esters particularly preferably poly (methyl methacrylate) or poly (cyclohexyl methacrylate), or copolymers of these polymers with other degradable polymers, such as preferably styrene / ethyl acrylate copolymers or methyl methacrylate / ethyl acrylate copolymers, and polyolefins, Polyolefin oxides, polyethylene terephthalate, polyformaldehyde, polyamides, polyvinyl acetate, polyvinyl chloride or polyvinyl alcohol.
  • the core consists of polymers which can be degraded by UV radiation.
  • polymers which can be degraded by UV radiation Particularly worth mentioning here are poly (tert-butyl methacrylate), poly (methyl methacrylate), poly (n-butyl methacrylate) and copolymers which contain one of these polymers.
  • MW Perpall K. Prasanna, U. Perera, J. DiMaio, J. Ballato, St.H. Foulger, DW Smith, Langmuir 2003, 19, 7153-7156 describe a manufacturing method for inverse pale from vitreous carbon.
  • an opal structure is made from silica particles and crosslinked by sintering. Then the opal pores are soaked with bis (ortho-divinylbenzene) monomers, these are cured, the Si0 2 removed by HF etching and the matrix subsequently burned to carbon.
  • the associated process can be managed economically due to the possible production speed and the low energy costs compared to similar known processes
  • the jacket polymers can intertwine and thus mechanically stabilize the regular arrangement of balls in the template
  • the templates can be processed via melting processes, the resulting shaped articles are characterized by high mechanical strength, in particular tensile strength,
  • the resulting shaped bodies can be used without an additional carrier due to their mechanical stability, -
  • the resulting shaped bodies with ellipsoidal pores can be produced in a targeted manner and used in particular to utilize anisotropic effects as a photonic material.
  • Shaped bodies with regularly arranged cavities which are embedded in a carbon matrix and which are characterized in that they can be obtained by the process according to the invention are therefore also used.
  • the core-shell particles In order to achieve the optical or photonic effect according to the invention, it is desirable for the core-shell particles to have an average particle diameter in the range from approximately 5 nm to approximately 2000 nm. It can be particularly preferred if the core-shell particles have an average particle diameter in the range from about 5 to 20 nm, preferably 5 to 10 nm. In this case the nuclei can be called "quantum dots"; they show the corresponding effects known from the literature. To achieve color effects in the range of visible light, it is particularly advantageous if the core-shell particles have an average particle diameter in the range of approximately 50-800 nm.
  • Particles in the range from 100 to 600 nm and very particularly preferably in the range from 200 to 450 nm are particularly preferably used, since with particles in this order of magnitude (depending on the refractive index contrast which can be achieved in the photonic structure) the reflections of different wavelengths of visible light become clear distinguish from each other and so the opalescence, which is particularly important for optical effects in the visible range, occurs particularly distinctly in a wide variety of colors. In a variant of the present invention, however, it is also preferred to use multiples of this preferred particle size, which then lead to reflections corresponding to the higher orders and thus to a broad play of colors.
  • the cavities of the shaped bodies according to the invention then each have corresponding average diameters, which are approximately identical to the diameter of the cores. With preferred core-shell ratios of the particles, the cavity diameter thus corresponds to approximately 2/3 of the core-shell particle diameter. It is particularly preferred according to the invention if the mean diameter of the cavities in the
  • Range of about 50-500 nm preferably in the range of 100-500 nm and very particularly preferably in the range of 200 to 280 nm.
  • the cavities are not spherical, but have an anisotropy (cf. FIG. 1). Corresponding moldings with aligned ellipsoidal cavities are therefore a further subject of the present invention.
  • ellipsoid means that the pores in at least one spatial direction have a different diameter than in the other spatial directions and are consequently not spherical.
  • Aligned means that the spatial orientation of the pores is such that the deviating diameters in different pores are approximately parallel to one another.
  • the template material can first be annealed at a temperature below the decomposition temperature of the cores.
  • the intermediate layer is a preferred one
  • Embodiment of the invention around a layer of crosslinked or at least partially crosslinked polymers can be crosslinked via free radicals, for example induced by UV radiation, or preferably via di- or oligofunctional monomers.
  • Preferred intermediate layers of this embodiment contain 0.01 to 100% by weight, particularly preferably 0.25 to 10% by weight, di- or oligo-functional monomers.
  • Preferred di- or oligo-functional monomers are in particular isoprene and allyl methacrylate (ALMA).
  • AMA allyl methacrylate
  • Such an intermediate layer of crosslinked or at least partially crosslinked polymers preferably has a thickness in the range from 10 to 20 nm. If the intermediate layer is thicker, the refractive index of the layer is selected such that it corresponds either to the refractive index of the core or to the refractive index of the cladding.
  • copolymers are used as the intermediate layer which, as described above, contain a crosslinkable monomer
  • the person skilled in the art will have no problem in selecting suitable copolymerizable monomers in a suitable manner.
  • corresponding copolymerizable monomers can be selected from a so-called Q-e scheme (cf. textbooks of macromolecular chemistry).
  • Monomers such as methyl methacrylate and methyl acrylate can preferably be polymerized with ALMA. In this case, the intermediate layer can be broken down together with the core.
  • shell polymers are directly, via a appropriate functionalization of the core, grafted onto the core.
  • the surface functionalization of the core forms the intermediate layer according to the invention.
  • the shell of this core is a preferred embodiment, the shell of this core
  • Sheath particles made from essentially uncrosslinked organic polymers, which are preferably grafted onto the core via an at least partially crosslinked intermediate layer.
  • the core can come from a wide variety
  • the core of the core-shell particles consists of a material which either does not flow or becomes flowable at a temperature above the flow temperature of the shell material.
  • This can be achieved by using polymeric materials with a correspondingly high glass transition temperature (T g ), preferably cross-linked polymers.
  • the wall of the shaped body with, regularly arranged cavities 5 is formed from the above described carbon matrix.
  • a “positive” opal structure is formed as a template in a first step by applying a mechanical force to the core-shell particles.
  • the mechanical action of force can, according to the invention, be such a force action that occurs in the usual processing steps of polymers.
  • the mechanical force is applied either: by uniaxial pressing or
  • the shaped bodies according to the invention are preferably films. Films according to the invention can preferably also be produced by calendering, film blowing or flat film extrusion.
  • the various possibilities of processing polymers under the influence of mechanical forces are well known to the person skilled in the art and can be found, for example, in the standard textbook Adolf Franck, "Plastic Compendium”; Vogel-Verlag; 1996 are taken.
  • the processing of core-shell particles by the action of mechanical force, as is preferred here, is also described in detail in the international patent application WO 2003025035.
  • the temperature during production is at least 40 ° C., preferably at least 60 ° C., above the glass point of the shell of the core-shell particles. It has been shown empirically that the flowability of the jacket in this temperature range particularly meets the requirements for economical production of the shaped bodies.
  • the flowable core-shell particles are cooled under the action of the mechanical force to a temperature at which the shell is no longer flowable. If moldings are produced by injection molding, it is particularly preferred if the demolding takes place only after the mold with the molding contained therein has cooled. In the technical implementation, it is advantageous if molds with a large cooling channel cross section are used, since the cooling can then take place in a shorter time. It has been shown that the color effects according to the invention become significantly more intense as a result of the cooling in the mold. It is assumed that this uniform cooling process leads to a better arrangement of the core-shell particles with the lattice. It is particularly advantageous if the mold was heated before the injection process.
  • the moldings according to the invention can, if it is technically advantageous, contain auxiliaries and additives. They can be used to optimally set the application data or properties desired or required for application and processing.
  • auxiliaries and / or additives are antioxidants, UV stabilizers, biocides, plasticizers, film-forming aids, leveling agents, fillers, melting aids, adhesives, release agents, application aids, mold release aids, agents for viscosity modification, e.g. B. thickener.
  • n is a number from 2 to 4, preferably 2 or 3, and m is a number from 0 to 500.
  • the number n can vary within the chain and the various chain links can be built in in a statistical or block-wise distribution.
  • auxiliaries are ethylene glycol, propylene glycol, di-, tri- and
  • Tetraethylene glycol di-, tri- and tetrapropylene glycol, polyethylene oxides
  • ethylene oxide and propylene oxide assemblies Molecular weights up to approx. 15000 and statistical or block-like distribution of the ethylene oxide and propylene oxide assemblies.
  • organic or inorganic solvents, dispersants or diluents which, for example, extend the open time of the formulation, ie the time available for its application to substrates, are also possible, waxes or hot-melt adhesives as additives.
  • z. B derivatives of 2,4-dihydroxybenzophenone, derivatives of 2-cyano-3,3'-dephenyl acrylate, derivatives of 2,2 ', 4,4'-tetrahydroxybenzophenone, derivatives of o-hydroxyphenyl-benzotriazole, salicylic acid esters, o-hydroxyphenyl -s-triazines or sterically hindered amines. These substances can also be used individually or as mixtures.
  • the total amount of auxiliaries and / or additives is up to 40% by weight, preferably up to 20% by weight, particularly preferably up to 5% by weight, of the weight of the moldings.
  • the cores can be removed in various ways. In a method preferred according to the invention, the removal of the
  • the process step itself can be the end products within the meaning of the present invention.
  • the carbon matrix can best be described as a structure containing a conductor polymer.
  • polyimides are formed, for example, according to the following scheme:
  • the carbon matrix is produced at temperatures in the range from 700 to 1200 ° C., preferably in the range from 800 to 1000 ° C., with the exclusion of air.
  • the resulting carbon matrix will rather be described as an amorphous, partially crystalline or crystalline carbon material, in particular as a graphite-like carbon material.
  • the cavities of the moldings can be impregnated with liquid or gaseous materials.
  • the impregnation can consist, for example, of storing liquid crystals, as described, for example, in Ozaki et al., Adv. Mater. 2002, 14, 514 and Sato et al.,
  • Electro-optical polymers can also be embedded in the cavities.
  • the impregnation with such or other materials allows the optical, electrical, acoustic and mechanical properties to be influenced by external energy fields.
  • optical, electrical, acoustic and mechanical properties can be influenced by external energy fields.
  • the difference in refractive index between the matrix and the pores filled with liquid crystalline material changes when the liquid crystals are aligned in an electrical field.
  • the reflection or transmission of certain wavelengths can thus be switched electrically and can thus be used for the optical transmission of data.
  • electro-optical devices By means of a locally addressable control using the external field, it is possible to manufacture electro-optical devices in this way.
  • the use of the shaped bodies according to the invention with regularly arranged cavities for the production of electro-optical devices and electro-optical devices containing the shaped bodies according to the invention are therefore further objects of the present invention.
  • Electro-optical devices based on liquid crystals are well known to the person skilled in the art and can be based on various effects. Such devices are, for example, cells with dynamic scattering, DAP cells (deformation of aligned phases), guest / host cells, TN cells with a twisted nematic ("twisted nematic") structure, STN cells ("super-twisted nematic”), SBE cells ("superbirefringence effect”) and OMI cells ("optical mode interference”).
  • the most common display devices are based on the Schadt-Helfrich effect and have a twisted nematic structure.
  • the corresponding liquid crystal materials must have good chemical and thermal stability and good stability against electric fields and electromagnetic radiation. Furthermore, the liquid crystal materials should have a low viscosity and give short response times, low threshold voltages and a high contrast in the cells.
  • nematic or cholesteric mesophase for the above-mentioned cells.
  • liquid crystals are generally used as mixtures of several components, it is important that the components are readily miscible with one another.
  • Other properties, such as the electrical conductivity, the dielectric anisotropy and optical anisotropy must meet different requirements depending on the cell type and application. For example, materials for cells with a twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity.
  • media with large positive dielectric anisotropy, relatively low birefringence, wide nematic phases, very high resistivity, good UV and temperature stability and low vapor pressure are desired for matrix liquid crystal displays with integrated non-linear elements for switching individual pixels (MLC displays).
  • active elements i.e. transistors
  • MOS Metal Oxide Semiconductor
  • TFT Thin film transistors
  • the TN effect is usually used as the electro-optical effect.
  • TFTs based on polycrystalline or amorphous silicon. The latter technology is being worked on with great intensity worldwide.
  • the TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counter electrode on the inside. Compared to the size of the pixel electrode, the TFT is very small and practically does not disturb the image. This
  • Technology can also be expanded for fully color-compatible image representations, whereby a mosaic of red, green and blue filters is arranged in such a way that one filter element each is opposite a switchable image element.
  • the TFT displays usually work as TN cells with crossed polarizers in transmission and are illuminated from behind.
  • MLC displays of this type are particularly suitable for TV applications (e.g. pocket TVs) or for high-information displays for computer applications (laptops) and in automobile or aircraft construction.
  • TV applications e.g. pocket TVs
  • high-information displays for computer applications (laptops)
  • automobile or aircraft construction With decreasing resistance, the contrast of an MLC display deteriorates and the problem of "after image elimination” can occur.5
  • the specific resistance of the liquid crystal mixture generally decreases over the lifetime of an MLC display due to interaction with the inner surfaces of the display, a high (initial) resistance is very important in order to obtain acceptable service life. 0
  • the moldings according to the invention can in principle be used in combination with suitable liquid crystal mixtures known to the person skilled in the art in electro-optical displays based on all the principles described.
  • the shaped bodies obtainable according to the invention with regularly arranged cavities are suitable on the one hand for the use described above as photonic material, preferably with the impregnation mentioned, and on the other hand also for the production of porous surfaces, membranes, separators, filters and porous supports. These materials can also be used, for example, in fluidized bed reactors as a barrier membrane or fluidized bed.
  • Another application of the moldings described here is catalysis; the moldings according to the invention can serve as supports for catalysts. Use in chromatography as a stationary phase is also one of the possible uses according to the invention.
  • Biological and chemical sensors can also be produced using the moldings obtainable according to the invention with regularly arranged cavities if the pores are provided with suitable functional components, such as detection reagents, antibodies, enzyme substrates, DNA or RNA squenzies or proteins, by means of suitable surface treatment.
  • suitable functional components such as detection reagents, antibodies, enzyme substrates, DNA or RNA squenzies or proteins, by means of suitable surface treatment.
  • the weight ratio of core to shell is in the range from 5: 1 to 1:10, in particular in the range from 2: 1 to 1: 5 and particularly preferred is in the range 1, 5: 1 to 1: 2.
  • the core-shell particles which can be used according to the invention can be produced by various processes.
  • a preferred way of obtaining the particles is a process for the production of core-shell particles, by a) surface treatment of monodisperse cores, and b) application of the shell from organic polymers to the treated cores.
  • a crosslinked polymeric intermediate layer preferably by emulsion polymerization or by ATR polymerization, is applied to the cores, which is preferably reactive
  • ATR-Polymerization stands here for Atomic Transfer Radicalic Polymerization, as for example in K. Matyjaszewski, Practical Atom Transfer Radical Polymerization, Polym. Mater. Be. Closely. 2001, 84. Encapsulation of inorganic materials using ATRP is described, for example, in T. Werne, T. E. Patten, Atom Transfer
  • the liquid reaction medium in which the polymerizations or copolymerizations can be carried out consists of the solvents, dispersants or diluents customarily used in polymerizations, in particular in processes of emulsion polymerization. The selection is made so that the for
  • Emulsifiers can develop sufficient effectiveness.
  • a liquid reaction medium for carrying out the invention a liquid reaction medium for carrying out the invention
  • polymerization initiators are suitable which either decompose thermally or photochemically, form free radicals and thus initiate the polymerization.
  • thermally activatable polymerization initiators preference is given to those which decompose between 20 and 180 ° C., in particular between 20 and 80 ° C.
  • Particularly preferred polymerization initiators are peroxides, such as dibenzoyl peroxide, di-tert-butyl peroxide, peresters, percarbonates, perketals, hydroperoxides, but also inorganic peroxides, such as H 2 O 2 , salts of peroxosulfuric acid and peroxodisulfuric acid, azo compounds, boralkyl compounds and homolytically decomposing hydrocarbons.
  • the initiators and / or photoinitiators which, depending on the requirements of the polymerized material, are used in amounts between 0.01 and 15% by weight, based on the polymerizable components, can be used individually or in combination to take advantage of advantageous synergistic effects be applied.
  • redox systems are used, such as salts of peroxodisulfuric acid and peroxosulfuric acid in combination with low-valent sulfur compounds, especially ammonium peroxodisulfate in combination with sodium dithionite.
  • Polyaddition products are obtained analogously by reaction with compounds which have at least two, preferably three reactive groups, such as, for. B. epoxy, cyanate, isocyanate, or isothiocyanate have groups, with compounds that carry complementary reactive groups.
  • epoxy, cyanate, isocyanate, or isothiocyanate have groups, with compounds that carry complementary reactive groups.
  • isocyanates react with alcohols to form urethanes, with amines to form urea derivatives, while epoxides react with these complementaries to form hydroxyethers or hydroxyamines.
  • polyaddition reactions can advantageously also be carried out in an inert solvent or dispersant.
  • Dispersing aids are generally used to prepare the stable dispersions required for these polymerization-polycondensation or polyaddition processes.
  • Water-soluble, high molecular weight organic compounds with polar groups such as polyvinyl pyrrolidone, copolymers of vinyl propionate or acetate and vinyl pyrrolidone, partially saponified copolymer list of an acrylic ester and acrylonitrile, polyvinyl alcohols with different residual acetate content, cellulose ethers, gelatin, block copolymers, are preferably used as dispersants Starch, low molecular weight, carbon and / or sulfonic acid group-containing polymers or mixtures of these substances are used.
  • polar groups such as polyvinyl pyrrolidone, copolymers of vinyl propionate or acetate and vinyl pyrrolidone, partially saponified copolymer list of an acrylic ester and acrylonitrile, polyvinyl alcohols with different residual acetate content, cellulose ethers, gelatin, block copolymers, are preferably used as dispersants Starch, low molecular weight, carbon and / or
  • Particularly preferred protective colloids are polyvinyl alcohols with a residual acetate content of less than 35, in particular 5 to 39 mol% and / or vinylpyrrolidone-aminopropionate copolymers with a vinyl ester content of less than 35, in particular 5 to 30% by weight.
  • Nonionic or ionic emulsifiers can be used.
  • Preferred emulsifiers are, where appropriate, ethoxylated or propoxylated, longer-chain alkanols or alkylphenols with different degrees of ethoxylation or propoxylation (eg adducts with 0 to 50 mol of alkylene oxide) or their neutralized, sulfated, sulfonated or phosphated derivatives.
  • Neutralized dialkyl sulfosuccinic acid esters or alkyl diphenyl oxide disulfonates are particularly suitable.
  • Dispersions can be obtained.
  • the particle size can be set, for example, via the selection and amount of the initiators and other parameters, such as the reaction temperature. The appropriate setting of these parameters does not pose any difficulties for the person skilled in the field of polymerization.
  • Jacket made of organic polymers by grafting, preferably by emulsion polymerization or ATR polymerization.
  • the methods and monomers described above can be used accordingly.
  • a template emulsion tempered to 4 ° C. consisting of 217 g of water, 0.4 g of allyl methacrylate (ALMA, MERCK), 3.6 g of methyl methacrylate (MMA, MERCK) and 20.5 mg of sodium dodecylsulaft (SDS , MERCK), 30 mg of sodium dithionite (SDTH, MERCK), dissolved in 5 g of water, are added.
  • the emulsion is transferred to a 1-1-jacketed stirred tank temperature-controlled at 75 ° C. with a reflux condenser, argon gas inlet and a double propeller stirrer.
  • the reaction is started by adding 150 mg of ammonium peroxodisulfate (APS, MERCK) and a further 30 mg of sodium dithionite (SDTH, MERCK), each dissolved in 5 g of water.
  • APS ammonium peroxodisulfate
  • SDTH sodium dithionite
  • a monomer emulsion consisting of 9.6 g ALMA (MERCK), 96 g MMA (MERCK), 0.35 g SDS (MERCK), 0.1 g KOH (MERCK) is and 130 g of water were metered in continuously over a period of 120 min using a wobble piston pump. The reactor contents are stirred for 60 minutes without further addition. Then 100 mg of APS (MERCK), dissolved in 5 g of water, are added.
  • a second monomer emulsion consisting of 60 g of styrene (from MERCK), 60 g of acrylonitrile, 0.33 g of SDS (from MERCK) and 120 g of water is metered in continuously over a period of 160 minutes using a wobble piston pump ,
  • the core-shell particles are then coagulated in 11 methanol, the precipitation by adding 25 g of concentrated aqueous Saline completed, the suspension with 1 I of dest. Water is added, filtered off with suction and the polymeric coagulate is dried at 50 ° C. in vacuo.
  • the master emulsion contains 22 mg SDS (MERCK), the second monomer emulsion consists of 36 g styrene (MERCK), 84 g acrylonitrile, 120 g water, 0.4 g SDS (MERCK) and 0.34 g Triton X405 TM.
  • the coagulate consisting of PMMA-PSAN 50 latex particles, is processed in a DSM microextruder at 220 ° C in a nitrogen atmosphere to a polymer strand that is cut into 5 mm long granules. The granules are pressed into films.
  • the films obtained have a thickness of approx. 0.2 mm, have an angle-dependent, yellow-green color when viewed vertically and are tough and elastic.
  • the films are pyrolyzed in an air atmosphere at 240 ° C. in a muffle furnace for 5 hours.
  • the pyrolyzed films have a black base color, which is superimposed on a violet reflection color when viewed vertically. The latter is caused by the inverse opaline structure of the films, which can be seen in FIG. 1.
  • the pores in the film have a rather elliptical shape, as can be seen in FIG. 1.
  • the films are annealed in an air atmosphere at 200 ° C for 2 weeks.
  • the annealed films, in which the polymer cores are still present, have a brown base color and a green one
  • the films are then in an air atmosphere at 240 ° C in
  • the pyrolyzed films have a black base color and a purple one

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Graft Or Block Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne l'utilisation de particules à noyau et enveloppe, particules dont le noyau est essentiellement constitué d'un polymère dégradable et présente une distribution des tailles sensiblement dispersée, et dont l'enveloppe forme une matrice qui peut subir une pyrolyse pour former une matrice de carbone, pour la production de corps façonnés présentant des cavités disposées de façon régulière. L'invention concerne également les corps façonnés correspondants.
EP04797749A 2003-12-10 2004-11-10 Utilisation de particules a noyau et enveloppe Withdrawn EP1727839A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE10357681A DE10357681A1 (de) 2003-12-10 2003-12-10 Verwendung von Kern-Mantel-Partikeln
PCT/EP2004/012677 WO2005056622A1 (fr) 2003-12-10 2004-11-10 Utilisation de particules a noyau et enveloppe

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EP1727839A1 true EP1727839A1 (fr) 2006-12-06

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EP (1) EP1727839A1 (fr)
DE (1) DE10357681A1 (fr)
TW (1) TW200528495A (fr)
WO (1) WO2005056622A1 (fr)

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JP4093532B2 (ja) * 2001-03-13 2008-06-04 独立行政法人理化学研究所 アモルファス状金属酸化物の薄膜材料の製造方法
DE10245848A1 (de) * 2002-09-30 2004-04-01 Merck Patent Gmbh Verfahren zur Herstellung inverser opalartiger Strukturen
DE102006055522A1 (de) * 2006-11-24 2008-05-29 Robert Bosch Gmbh Zusammensetzung zur Herstellung eines keramischen Materials, enthaltend porenbildende Nanopartikel
DE102009000813A1 (de) 2009-02-12 2010-08-19 Evonik Degussa Gmbh Fluoreszenzkonversionssolarzelle I Herstellung im Plattengußverfahren
DE102009002386A1 (de) 2009-04-15 2010-10-21 Evonik Degussa Gmbh Fluoreszenzkonversionssolarzelle - Herstellung im Spritzgussverfahren
DE102009027431A1 (de) 2009-07-02 2011-01-05 Evonik Degussa Gmbh Fluoreszenzkonversionssolarzelle - Herstellung im Extrusionsverfahren oder im Coextrusionsverfahren
GB2472987A (en) 2009-08-24 2011-03-02 Cambridge Entpr Ltd Composite optical materials, uses of composite optical materials and methods for the manufacture of composite optical materials
DE102010028186A1 (de) 2010-04-26 2011-10-27 Evonik Röhm Gmbh Fluoreszenzkonversionssolarzelle Lacke
DE102010028180A1 (de) 2010-04-26 2011-10-27 Evonik Röhm Gmbh Fluoreszenzkonversionssolarzelle - Herstellung im Extrusionslaminationsverfahren oder im Kleberlaminationsverfahren
DE102010038685A1 (de) 2010-07-30 2012-02-02 Evonik Röhm Gmbh Fluoreszenzkonversionssolarzelle Herstellung im Plattengußverfahren
CN103534079B (zh) 2011-01-12 2016-02-03 剑桥企业有限公司 复合光学材料的制造
US9228717B2 (en) * 2013-11-28 2016-01-05 Lg Display Co., Ltd. Quantum rod compound including electron acceptor and quantum rod luminescent display device including the same
KR102253391B1 (ko) * 2013-11-28 2021-05-20 엘지디스플레이 주식회사 전자 수용체를 구비한 퀀텀로드 화합물과 이를 이용한 퀀텀로드 표시장치
WO2018230706A1 (fr) * 2017-06-16 2018-12-20 住友電気工業株式会社 Fil électrique isolé
JP2019043975A (ja) * 2017-08-29 2019-03-22 住友化学株式会社 コアシェル型粒子
CN109179379B (zh) * 2018-11-01 2021-11-30 中山大学 一种具有碳纳米管核@功能无定形碳壳单元的纳米网络结构碳材料及其制备方法和应用
CN116621582B (zh) * 2023-05-04 2024-06-04 中国海洋大学 一种具有蜂窝状多孔结构的碳材料及其制备方法与它的用途

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5029837B2 (fr) * 1971-09-01 1975-09-26
US4025689A (en) * 1971-09-01 1977-05-24 Agency Of Industrial Science & Technology Method for manufacture of graphitized hollow spheres and hollow spheres manufactured thereby
DE10228228A1 (de) * 2001-09-14 2003-04-03 Merck Patent Gmbh Formkörper aus Kern-Mantel-Partikeln
CA2459749A1 (fr) * 2001-09-14 2003-03-27 Merck Patent Gesellschaft Mit Beschraenkter Haftung Corps moule a partir de particules noyau-envelopppe
DE10245848A1 (de) * 2002-09-30 2004-04-01 Merck Patent Gmbh Verfahren zur Herstellung inverser opalartiger Strukturen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2005056622A1 *

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US20070160521A1 (en) 2007-07-12
DE10357681A1 (de) 2005-07-21
TW200528495A (en) 2005-09-01

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