EP1694780A2 - Fonctionnalisation de la surface de particules oxydiques, particules a surface ainsi fonctionnalisee et leur utilisation - Google Patents

Fonctionnalisation de la surface de particules oxydiques, particules a surface ainsi fonctionnalisee et leur utilisation

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Publication number
EP1694780A2
EP1694780A2 EP04803936A EP04803936A EP1694780A2 EP 1694780 A2 EP1694780 A2 EP 1694780A2 EP 04803936 A EP04803936 A EP 04803936A EP 04803936 A EP04803936 A EP 04803936A EP 1694780 A2 EP1694780 A2 EP 1694780A2
Authority
EP
European Patent Office
Prior art keywords
particles
groups
silicon
reaction step
halogen
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Withdrawn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
EP04803936A
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German (de)
English (en)
Inventor
Michael Binnewies
Thomas Giesenberg
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1694780A2 publication Critical patent/EP1694780A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • 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
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3653—Treatment with inorganic 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
    • C09C1/36—Compounds of titanium
    • C09C1/3692—Combinations of treatments provided for in groups C09C1/3615 - C09C1/3684
    • 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
    • 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
    • C09C3/06—Treatment with inorganic compounds
    • C09C3/063—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • 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
    • C01P2006/12—Surface area
    • 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
    • C01P2006/42—Magnetic properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • 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.]

Definitions

  • the invention relates to a method for the functionalization of surfaces of amorphous or crystalline compounds (particles) which on the one hand contain a metal or semimetal which is not exclusively silicon and on the other hand contain oxygen.
  • the invention further relates to particles which can be obtained in this way and their different possible uses.
  • Inorganic particles come e.g. as reinforcing fillers, catalysts, catalyst supports, pigments, materials with special mechanical, electrical, dielectric, magnetic or optical properties.
  • the surface quality of the inorganic particles is of central importance for their use in inorganic / organic hybrid materials.
  • the invention describes a method which makes it possible to chemically change the surfaces of particles of the composition described, preferably oxides, particularly preferably metal oxides, in such a way that they optimally correspond to the particular intended use.
  • the surface modification can consist of a so-called hydrophobization.
  • the oxidic surfaces are coated with organic compounds in such a way that non-polar groups of the organic compounds lie on the particle surface.
  • this is achieved by reacting the oxidic particles with alcohols, alcoholates, carboxylic acids, carboxylic acid chlorides or with organosilicon compounds.
  • EP-A-1 284 277 describes metal oxide particles coated with silicon dioxide. These are prepared by adding a base dissolved in water with stirring to a dispersion which contains a metal oxide and a compound of the type X n Si (OR) -n . The reaction product is separated from the water phase, optionally washed and dried.
  • the metal oxides can, for example, titanium dioxide, zinc oxide, zirconium oxide, iron oxide, cerium oxide or Mixtures of these metal oxides with alumina or silica.
  • the particles obtainable in this way are suitable, for example, as sunscreens, as UV filters, for the production of dispersions and in processes for chemical mechanical polishing.
  • the object of the present invention is to functionalize oxidic particles other than silicon dioxide particles to a much greater extent than is possible according to the prior art.
  • This object is achieved by applying a layer of silicon / oxygen / halogen compounds, preferably silicon / oxygen / chlorine, according to the invention.
  • the thickness of the layer applied according to the invention can be up to one micrometer.
  • the functionality of the layer is achieved in that the silicon atoms fixed on the particle surface according to the invention are still bound to one to three chlorine atoms. These in turn can be replaced in a simple manner by practically any other substituents, preferably organic radicals. For example, the substitution of all or part of the chlorine atoms by long-chain hydrocarbon residues leads to hydrophobic particles which prefer the organic phase in water toluene.
  • a functionalized particle according to the invention can also carry 2, 3 or more functionally different functional groups.
  • the particles as semimetal M should not exclusively contain silicon means that they should not consist of silicon dioxide or “silicas”.
  • the metallic or semimetallic component M can consist partly of silicon, as is the case, for example, with aluminosilicate minerals.
  • Such compounds such as, for example, layered silicates such as mica, bentonites etc., are encompassed by the present invention, further, non-exhaustive examples of the oxidic compounds encompassed by the invention are titanium dioxide, zirconium oxides, zinc oxide, iron oxides, nickel oxides, manganese oxides, cerium oxides, aluminum oxides or else mixed oxides that contain the metals titanium, zinc, zircon, iron, cobalt, nickel, cerium and / or aluminum.
  • the number of MOH groups on the particle surface can be increased by that the particle surface in a reaction step b) preceding reaction step a) in contact with a strong acid. This is preferably done in the aqueous phase and under conditions in which the oxide particles are attacked on the surface but not dissolved. Variable parameters for this are in particular the strength of the acid, the reaction temperature and the reaction time. Suitable strong acids here are acids of the strength of phosphoric acid and stronger acids such as, in particular, sulfuric acid. After the surface reaction with the acid, the particles are preferably washed before reaction step b) and then dried.
  • the silicon-halogen compounds which are brought into contact with the oxidic particles in reaction step b) are preferably selected from silicon chlorides and silicon bromides, for example from silicon tetrachloride and silicon tetrabromide.
  • the reaction is preferably carried out in the liquid phase, but in an environment which is as anhydrous as possible.
  • the liquid phase should therefore contain as little water as technically possible.
  • the water content should be below 1 ppm. This ensures that the Si-halogen bonds are not hydrolyzed by water, or at least only to a minor extent, while the majority of the silicon-halogen molecules are bound to the particle surface by reaction with the superficial M-O-H groups.
  • the reaction is preferably controlled such that 1 to 3 M-O-Si bonds are formed per silicon atom, while 3 to 1, preferably 1 to 2, Si-halogen bonds are retained. These are then available for further functionalization reactions.
  • the silicon-halogen compounds that are to be reacted with the oxidic particles are suitable as the liquid phase. So these serve not only as a reagent, but also as a reaction medium.
  • the silicon-halogen compounds can also be brought into contact with the particles of the oxidic compounds in dry, non-protic solvents. Examples of suitable non-protic solvents are cyclohexane and diethyl ether. Liquid aromatic or aliphatic hydrocarbons, such as, for example, benzene, toluene or petroleum ether, are suitable as further non-protic solvents.
  • Such a further functionalization reaction can consist in contacting the particles coated with a layer of silicon-halogen compounds in reaction step b) in a further reaction step c) with water under conditions such that the MO-Si-X groupings react to form MO-Si-OH groups.
  • the "silicatisation" of the surface achieved in this way can be achieved can also be achieved with methods according to the state of the art, however, by the upstream reaction with silicon-halogen compounds in reaction step b), the occupancy density becomes significantly higher than according to conventional methods, for example than according to the method of EP-A-1 284 277.
  • a further reaction step d) the particles obtained with their superficial M-O-Si-OH groups can again be brought into contact with the silicon-halogen compounds as described above.
  • M-O-Si-O-Si-X groups (where X represents the corresponding halogen atom) are obtained in this way with the formation of a second layer. In this way, the coating thickens, which can lead to higher chemical stability.
  • the two reaction steps c) and d) can now be repeated any number of times. This means that the Si-X groups newly added in reaction step d) can be hydrolyzed again with water, the Si-X bond being replaced by a Si-OH bond.
  • the next O-Si-X layer is then deposited by repeated reaction with silicon-halogen compounds in a further reaction step d).
  • any coating thickness can be built up in a targeted manner. Layer thicknesses can be achieved which are clearly above 25 nm, for example in the range from 50 nm to 1 ⁇ m and even beyond, for example up to 25 ⁇ m.
  • Reaction step c) do not repeat the Si-OH groupings obtained with the silicon
  • R represents an organic radical bonded to the Si via a C atom and, in the case of several R radicals in the molecule, these may be the same or different, under such conditions that the group Z is split off from the MO-Si-OH - Groups MO-Si-O-SiR n - form groups.
  • Z here means a hydrolyzable group bonded to silicon via oxygen, such as an alcoholate and in particular an ethanolate residue.
  • Another process alternative is that after reaction step b) or after a reaction step d) in a further reaction step e), the particles are brought into contact with at least one organic compound or a hydride source under conditions such that Si-X bonds are split and instead bonds form Si to the organic compound or to a residue thereof or to a hydrogen atom.
  • reaction step b) In order to prevent the Si-X bonds from being hydrolyzed to Si-OH bonds in this reaction step e), the reaction step b) must be carried out under conditions that are as low as possible in water.
  • the reaction conditions given above in reaction step b) apply accordingly to this reaction step e).
  • examples of corresponding reactions are mentioned which have been carried out on silicon dioxide particles which have surface Si-Cl groups.
  • the details given there can be applied in an analogous manner to the present invention, the particles of oxidic compounds precoated in the sub-step b) or d) replacing the silicon dioxide particles.
  • the two documents mentioned also contain further details of how the particles obtained after reaction step e) can be characterized more analytically.
  • reaction step e a mixture of different compounds can be used in reaction step e). This then leads to oxidic particles that have different organic residues on their surface. If a hydride source such as LiAIH 4 is used in reaction step e), the surface Si-X bonds are replaced by Si-H bonds.
  • a hydride source such as LiAIH 4
  • the reactants used are preferably either compounds which carry at least 1 acidic hydrogen atom or which have at least one positively polarized organic radical R.
  • organic compounds with an acidic hydrogen atom are alcohols, primary or secondary amines and primary or secondary phosphines.
  • reaction step e) is therefore preferably characterized in that the organic compound is selected from
  • the radical R can be a butadiene radical, which enables the appropriately coated particles to be incorporated into a rubber matrix.
  • the present invention relates generally to particles as can be obtained by the process described above.
  • the density of the silicon-containing groups per nm 2 surface is accordingly significantly higher than can be achieved with the oxidic particles according to the invention in the past.
  • the density of the silicon-containing groups on the surface is at least 5, in particular at least 6.
  • the achievable occupancy density of the surfaces can depend on the space requirement of the Y groups: the bulkier these groups are, the less space there is per nm 2 of surface. Conversely, with large residues Y, a smaller number of these residues per nm 2 surface are required in order to at least largely cover the surface.
  • the organic radicals Y are characterized by the number of their carbon atoms, particles according to the invention which are such a number of -Si-Y groups per nm 2 surface that at least 4, preferably at least 6 and in particular per nm 2 surface there are at least 8 carbon atoms of the organic radicals Y.
  • Particles which have at least 6 carbon atoms, at least 8 carbon atoms, at least 12 carbon atoms, at least 16 carbon atoms, at least 20 carbon atoms, at least 24 carbon atoms, at least 28 carbon atoms and at least 32 carbon atoms from the organic radicals Y are increasingly preferred per nm 2 surface.
  • thermogravimetric analysis and / or DSC measurement can also be used for the latter.
  • thermogravimetric Analysis with access to air burns the organic residues at elevated temperature, which leads to a loss of mass. This combustion reaction manifests itself in an exothermic effect in a DSC measurement.
  • the comparison can be made with a thermogravimetric analysis and / or DSC measurement of the starting substance not occupied by the silicon-containing groups.
  • the total number of organic residues in moles and thus the occupancy density can be determined from the weight loss.
  • This analysis can be supported or supplemented by capturing the carbon dioxide and water generated during the combustion of the organic residues in the sense of a combustion analysis and drawing conclusions from the amount collected on the number of organic residues. If the chemical nature of the organic residues and / or their number per Si atom is unknown in an unknown sample, at least the number of carbon atoms per nm 2 surface can be inferred from such analyzes. In addition, mass spectroscopic techniques can be used to determine the chemical nature of the organic residues.
  • the occupancy density can be calculated in groups per nm 2 . Further information on this can be found in the cited article by Giesenberg et al. as well as the EP patent application cited herein.
  • Booster filler Reinforcing fillers significantly improve the properties of organic polymers. Their effectiveness largely depends on the connection of the built-in inorganic particles to the surrounding, mostly organic matrix. Preference is given to those particles which have substituents on their surface which have a chemical similarity to the surrounding matrix, particularly preferred those which can form a firm covalent bond with the matrix. This can be achieved, for example, by the substituent on the surface of the particles being an unsaturated organic radical, very particularly preferably a radical which is the monomer of the surrounding polymer matrix.
  • catalysts for heterogeneous catalysis is largely determined by the size of their surface.
  • a firm connection of catalytically active atoms, molecules or particles to the surface of small particles is desirable.
  • Both "hard” atoms or groupings of atoms or "soft” atoms or groupings of atoms can be catalytically active (as defined by Pearsson).
  • amino groups on the surface of the particles are able to bind a “hard” atom and, for example, phophane groups are able to bind a “soft” atom.
  • the surface can be functionalized on particles of any size, morphology and specific surface.
  • pigment particles in paints and related products are not only determined by their optical properties, but also decisively by their dispersibility in and binding into the respective inorganic or organic medium.
  • the functionalization of the surface can also be carried out here on particles of any size, morphology and specific surface according to the respective requirements.
  • Particularly hard inorganic particles such as aluminum oxide (corundum) are used in the form of composite materials, for example as tools (for example grinding wheels), or as grinding or polishing agents.
  • the strength of the connection to the matrix or the abrasive medium exerts a very strong influence on the properties of the material.
  • the functionalization of the Depending on the respective requirements, the surface can also be made of particles of any size, morphology and specific surface.
  • ferro-, ferri-magnetic or superparamagnetic particles magnetic polymers, ferrofluids with a long service life and in particular medical technology applications: If it is possible to bind active substances to the surface of magnetic particles, these can in principle be achieved by a magnetic field can be directed to the areas of the body where they are supposed to work. Similar developments are also being carried out elsewhere, and the first particles are already commercially available. The path we have followed is connected with little effort, inexpensive and the connection of active substances to metal oxides modified in this way should be easy.
  • the particles produced according to the invention or according to the invention can be used in a variety of ways and can take the place of conventionally hydrophobicized or functionalized particles of oxidic compounds which are produced in a conventional manner and are therefore less strongly coated than the particles according to the present invention.
  • the present invention also covers the use of the particles produced or according to the invention for different applications or in different media.
  • the invention encompasses the use of such particles as a component of catalysts (e.g. as a carrier for the actually catalytically active components) or as chromatography materials.
  • the invention further comprises the use of such particles in compositions for application to skin or hair, for example in sunscreens.
  • preference is given to selecting oxidic particles which absorb UV radiation particularly strongly. Examples include titanium dioxide, tin dioxide and zinc oxide. Titanium dioxide in particular is a very good absorber for UV radiation.
  • it has the disadvantage of being photocatalytic when irradiated and triggering undesirable secondary reactions either on average or on the skin and / or hair. This undesirable property is strongly suppressed by the coating according to the invention.
  • the invention relates to the use of the particles produced or according to the invention in a matrix of organic polymers.
  • reactions can occur due to the undesired photocatalytic activity, which ultimately destroy the organic matrix.
  • the coating according to the invention considerably inhibits these reactions, so that the service life of the plastic part or of a lacquer containing titanium dioxide is significantly extended. When used as a reinforcer or filler, the increased coating density leads to improved tear strengths.
  • the invention further relates to the use of particles coated or according to the invention as abrasive components in abrasives or polishing agents.
  • the oxidic particles must have a hardness that makes them suitable for this purpose. Examples of this are aluminum oxides, in particular corundum. Because of the coating according to the invention, the oxidic particles can be dispersed much better in the matrix of the abrasive or polishing agent. They are more finely distributed and more firmly bonded than conventionally coated particles, which on the one hand extends the life of the corresponding abrasive or polishing agent and on the other hand achieves a more uniform grinding or polishing result due to the finer distribution of the abrasive particles. This reduces the roughness of the ground or polished surface.
  • the oxide particles have magnetic properties, as is the case with iron oxides (e.g. magnetite), nickel oxides and certain mixed oxides, they can be used as a magnetic component in a liquid, spreadable or solid magnetic preparation. In particular, they can be suspended in a carrier liquid, which contains a so-called ferrofluid. Magnetic forces allow these ferrofluids to be directed to the desired places where they are supposed to work. Such ferrofluids are known in the prior art.
  • the improved coating according to the invention leads to the magnetic particles being better kept in dispersion, so that ferrofluids stabilized against phase separation can be obtained.
  • the present invention comprises in a last aspect any material which contains distributed particles according to the invention or produced according to the invention. What these materials can be, for example, is evident from the possible uses mentioned above.
  • basic chemicals can be used in the method according to the invention.
  • special chemicals such as e.g. Organosilanes needed.
  • Basic chemicals such as e.g. Sulfuric acid, hydrochloric acid and silicon tetrachloride or silicon bromide as well as organic and organometallic reagents such as e.g. Alcohols, Grignard reagents and lithium-organic reagents are used. Since a large number of reagents can be used here for functionalization, many new functionalities on correspondingly described particle surfaces are accessible compared to the methods according to the prior art through the process according to the invention.
  • the pretreatment of the above-mentioned particles according to the invention enables the density of functional groups per nm 2 on the respective particle surfaces to be increased. This is achieved by etching the respective particles with appropriate inorganic acids. This step increases the number of OH groups on the particle surface, which in the following functionalization step lays the foundation for a dense covering of the respective surface with functional groups. This not only generates a higher degree of functionalities on the respective particle surface, which generally leads to an improvement in the properties of the respective particles for the corresponding area of application, but also serves to protect the particles from attack by other chemicals or substances. 3.
  • the particles are preferably treated with silicon tetrabromide or particularly preferably with silicon tetrachloride. By reaction of the OH groups on the respective particle surfaces with silicon tetrabromide or silicon tetrachloride, corresponding silicon-halogen bonds are generated in each case, which can further be substituted by other substituents, preferably organic radicals.
  • silicon dioxide By simply hydrolysing the silicon-halogen bonds with water and repeated reaction with silicon tetrabromide or silicon tetrachloride, a layer of silicon dioxide is built up one after the other on the particle surface. The layer thickness is controlled by the number of repetition units. A silicon dioxide layer generated in this way on the surface of the particles described above protects them from chemicals and other harmful influences.
  • OH groups are generated on the surface of the metal oxide particles or their number is increased.
  • the valences of the surface atoms must also be saturated.
  • oxides this is usually done by replacing O 2 " ions with OH " ions on the surface of the particles, the number of which can be very small. By etching the surface with acid, this number can be increased significantly.
  • Figure 2 Reaction path for silanization with trichloroalkyl silanes.
  • the oxidic materials are each dispersed in concentrated sulfuric acid and etched with stirring for 4 hours.
  • the solid through a glass frit is (Po. 3) separated from the sulfuric acid and then washed first several times with distilled water to pH 7, with diethyl ether and dried under vacuum (10 -2 mbar).
  • the dry solid thus prepared is then refluxed with silicon tetrachloride for 12 hours.
  • the reprocessing procedure is repeated as described above.
  • the intermediate product is then dispersed in cyclohexane under dry reaction conditions and reacted by slowly adding an excess of trichloroctylsilane. The reaction mixture is refluxed for 12 hours.
  • the product is separated on a glass frit (item 3) and then washed with 3 x 30 mL cyclohexane, 3 x 30 mL distilled water and 2 x 30 mL diethyl ether. After drying in vacuo (approx. 10 "2 mbar), a hydrophobic powder is present.
  • the dry solid eg titanium dioxide
  • silicon tetrachloride under reflux for 12 hours.
  • the SiCI 4 is removed by filtration under a protective gas and subsequent drying in vacuo (approx. 10 "2 mbar) and the solid thus modified is placed in a Schlenk flask for reaction with the alcohol.
  • the solid is suspended in THF, and octanol and 1/2 eq triethylamine (based on the octanol used) are added.
  • the suspension is refluxed under protective gas and with stirring for 12 h.
  • the occupancy of octanol residues was determined in this way with rutile (TiO 2 ) reacted with SiCl 4 and then with octanol.
  • the specific surface area (BET method) of the reaction product was 10 to 12 m 2 / g.
  • a combustion analysis showed a carbon content which, taking into account the experimental inaccuracy, could be converted into around 40 to 55 carbon atoms per nm 2 .
  • the occupancy density with octyl groups was therefore about 5 to 7 groups per nm 2 .
  • M (C) is the atomic mass of carbon (12 g / mol). In this case, the following applies:
  • N (octyl) 6.02-10 23 w (C) / (100-96) If this value is divided by the specific surface area F BET (m 2 / g), the number of octyl residues per m 2 is obtained , or, after division by (10 9 ) 2, the number of octyl residues per nm 2 . The following applies:
  • w (C) is to be inserted in% F and B _rr in m 2 /. 9

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

L'invention concerne un procédé de modification de la surface de particules constituées de composés oxydiques de métaux et/ou de semi-métaux M, dont la surface présente des groupes M-O-H et contenant, de façon non exhaustive, du silicium en tant que métal ou semi-métal. Selon ledit procédé, les particules sont mises en contact avec des composés silicium-halogène dans des conditions telles que les groupes M-O-H réagissent avec ces composés. L'invention concerne également des particules à surface modifiée obtenues selon ce procédé. Afin de générer des groupes (additionnels) M-O-H sur la surface, on peut prétraiter les particules avec un acide fort. Dans une étape suivante, les groupes Si-halogènes superficiels sont mis en réaction avec des composés réagissant de façon correspondante pour produire d'autres particules modifiées. Les particules selon l'invention peuvent aussi être caractérisées en ce qu'elles portent des groupes Si-OH, des groupes Si-X (X = halogène) et/ou des groupes Si-Y (Y = reste organique) en une densité d'au moins 2 de tels groupes par nm<2> de surface et/ou qu'au moins 4 atomes de carbone des restes organiques Y sont présents par nm<2> de surface. L'invention concerne aussi l'utilisation de telles particules en tant que composants dispersés dans divers matériaux destinés à différentes utilisations, ainsi que chaque matériau contenant de telles particules réparties.
EP04803936A 2003-12-19 2004-12-16 Fonctionnalisation de la surface de particules oxydiques, particules a surface ainsi fonctionnalisee et leur utilisation Withdrawn EP1694780A2 (fr)

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DE10359840 2003-12-19
PCT/EP2004/014323 WO2005061631A2 (fr) 2003-12-19 2004-12-16 Fonctionnalisation de la surface de particules oxydiques, particules a surface ainsi fonctionnalisee et leur utilisation

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EP1694780A2 true EP1694780A2 (fr) 2006-08-30

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US (1) US20070014917A1 (fr)
EP (1) EP1694780A2 (fr)
DE (1) DE102004027493A1 (fr)
WO (1) WO2005061631A2 (fr)

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DE102010035328A1 (de) 2010-08-24 2012-03-01 Continental Reifen Deutschland Gmbh Funktionalisierungsverfahren, damit erhaltene Partikel und deren Verwendung
DE102011015033B4 (de) 2011-03-25 2019-03-14 Audi Ag Verfahren zum Bestimmen eines Deichselwinkels
US9432258B2 (en) * 2011-06-06 2016-08-30 At&T Intellectual Property I, L.P. Methods and apparatus to configure virtual private mobile networks to reduce latency
DE102011112948B3 (de) 2011-09-13 2012-12-06 Gottfried Wilhelm Leibniz Universität Hannover Verfahren zur Verbesserung der elektrischen Leitfähigkeit von anorganischen Partikeln und deren Verwendung
DE102012100123A1 (de) 2012-01-09 2013-07-11 Contitech Ag Partikulärer Feststoff, Verfahren zu dessen Herstellung, Verwendung als Füllstoff und zugehöriger Artikel
KR102295365B1 (ko) 2014-12-31 2021-08-31 삼성전자주식회사 복합 음극 활물질, 그 제조방법, 이를 포함하는 음극 및 리튬이차전지
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US20070014917A1 (en) 2007-01-18
WO2005061631A2 (fr) 2005-07-07
DE102004027493A1 (de) 2005-09-22
WO2005061631A3 (fr) 2005-08-25

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