EP2129360A1 - Procédé de fabrication d'oxydes métalliques, hydroxydes métalliques et/ou oxydes-hydroxydes métalliques nanoparticulaires, modifiés en surface - Google Patents

Procédé de fabrication d'oxydes métalliques, hydroxydes métalliques et/ou oxydes-hydroxydes métalliques nanoparticulaires, modifiés en surface

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Publication number
EP2129360A1
EP2129360A1 EP08717951A EP08717951A EP2129360A1 EP 2129360 A1 EP2129360 A1 EP 2129360A1 EP 08717951 A EP08717951 A EP 08717951A EP 08717951 A EP08717951 A EP 08717951A EP 2129360 A1 EP2129360 A1 EP 2129360A1
Authority
EP
European Patent Office
Prior art keywords
metal
hydroxide
metal oxide
particles
zinc
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Withdrawn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
EP08717951A
Other languages
German (de)
English (en)
Inventor
Andrey Karpov
Hartmut Hibst
Jing Hu
Bernd Bechtloff
Hartwig Voss
Kerstin Schierle-Arndt
Valerie Andre
Jens Rieger
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP08717951A priority Critical patent/EP2129360A1/fr
Publication of EP2129360A1 publication Critical patent/EP2129360A1/fr
Withdrawn legal-status Critical Current

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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
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
    • A61K8/27—Zinc; Compounds thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/005—Antimicrobial preparations
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
    • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
    • C01B13/14—Methods for preparing oxides or hydroxides in general
    • C01B13/36—Methods for preparing oxides or hydroxides in general by precipitation reactions in aqueous solutions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • 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
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/028—Compounds containing only magnesium as metal
    • 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
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • 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
    • C09C1/22—Compounds of iron
    • C09C1/24—Oxides of iron
    • 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
    • C09C1/3676—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
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/413—Nanosized, i.e. having sizes below 100 nm
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/60—Particulates further characterized by their structure or composition
    • A61K2800/61—Surface treated
    • A61K2800/614—By macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • 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
    • C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
    • 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
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • 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
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • 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
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • 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 processes for the preparation of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide and of aqueous suspensions of these particles. Furthermore, the invention relates to the surface-modified nanoparticulate particles obtainable by these processes of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide and aqueous suspensions of these particles and their use for cosmetic sunscreen preparations, as a stabilizer in plastics and as an antimicrobial agent.
  • Metal oxides are used for a variety of purposes, such.
  • As a white pigment as a catalyst, as part of antibacterial skin protection creams and as an activator for the rubber vulcanization.
  • In cosmetic sunscreens there are finely divided zinc oxide or titanium dioxide as UV-absorbing pigments.
  • Nanoparticles are particles of the order of nanometers. Their size is in the transition region between atomic or monomolecular systems and continuous macroscopic structures. In addition to their usually very large surface, nanoparticles are characterized by particular physical and chemical properties, which differ significantly from those of larger particles. For example, nanoparticles often have a lower melting point, absorb light only at shorter wavelengths, and have different mechanical, electrical, and magnetic properties than macroscopic particles of the same material. By using nanoparticles as building blocks, many of these special properties can also be used for macroscopic materials (Winnacker / Kuchler, Chemical Engineering: Processes and Products, (Ed .: R. Dittmayer, W. Keim, G. Kreysa, A. Oberholz ), Vol. 2: New Technologies, Chapter 9, Wiley-VCH Verlag 2004).
  • nanoparticles refers to particles having a mean diameter of from 1 to 500 nm, determined by means of electron microscopy methods.
  • Nanoparticulate zinc oxide with particle sizes below about 100 nm is potentially suitable for use as a UV absorber in cosmetic sunscreen preparations or transparent organic-inorganic hybrid materials, plastics, paints and coatings.
  • a use for the protection of UV-sensitive organic pigments and as an antimicrobial agent is possible.
  • Particles, particle aggregates or agglomerates of zinc oxide which are greater than about 100 nm lead to scattered light effects and thus to an undesirable decrease in transparency in the visible light range.
  • the highest possible transparency in the visible wavelength range and the highest possible absorption in the range of the near ultraviolet light are desirable.
  • Nanoparticulate zinc oxide with particle sizes below about 5 nm show a blue shift of the absorption edge due to the size quantization effect (L.Brus, J. Phys. Chem. (1986), 90, 2555 to 2560) and are therefore suitable for use as UV absorbers in UV -A area less suitable.
  • finely divided metal oxides for example of zinc oxide
  • dry and wet processes The classical incineration method of zinc, known as the dry process (eg, Gmelin volume 32, 8th Ed., Supplementary Volume, pp. 772 et seq.), Produces aggregated particles with a broad size distribution.
  • dispersions having average particle sizes in the lower nanometer range can only be obtained from such powders with great difficulty by virtue of the shearing forces which can be achieved being too low.
  • Particularly finely divided zinc oxide is mainly produced wet-chemically by precipitation processes.
  • the precipitation in aqueous solution generally yields hydroxide and / or carbonate-containing materials which must be thermally converted to zinc oxide.
  • the thermal aftertreatment has a negative effect on fineness, since the particles are subjected to sintering processes which lead to the formation of micrometer-sized aggregates, which can only be broken down to the primary particles by grinding to an incomplete extent.
  • Nanoparticulate metal oxides can be obtained, for example, by the microemulsion method.
  • a solution of a metal alkoxide is added dropwise to a water-in-oil microemulsion.
  • the hydrolysis of the alkoxides to the nanoparticulate metal oxide takes place.
  • the disadvantages of this method are, in particular, that the metal alkoxides are expensive starting materials, that in addition emulsifiers must be used and that the preparation of the emulsions with droplet sizes in the nanometer range represents a complex process step.
  • nanoparticulate zinc oxide prepared by a precipitation reaction.
  • the nanoparticulate zinc oxide is prepared starting from a zinc acetate solution via an alkaline precipitation.
  • the centrifuged zinc oxide can be redispersed by addition of methylene chloride to a sol.
  • the zinc oxide dispersions prepared in this way have the disadvantage that they have no good long-term stability owing to the lack of surface modification.
  • WO 00/50503 zinc oxide gels are described which contain nanoparticulate zinc oxide with a particle diameter of ⁇ 15 nm and which are redispersible to sols.
  • the solids produced by basic hydrolysis of a zinc compound in alcohol or in an alcohol / water mixture are redispersed by the addition of dichloromethane or chloroform.
  • the disadvantage here is that no stable dispersions are obtained in water or in aqueous dispersants.
  • WO 93/21127 describes a process for producing surface-modified nanoparticulate ceramic powders.
  • a nanoparticulate ceramic powder is surface-modified by applying a low molecular weight organic compound, for example, propionic acid.
  • a low molecular weight organic compound for example, propionic acid.
  • This method can not be used for the surface modification of zinc oxide, since the modification reactions are carried out in aqueous solution and zinc oxide dissolves in aqueous organic acids. Therefore, this method can not be used for the production of zinc oxide dispersions;
  • zinc oxide in this application is also not mentioned as a possible starting material for nanoparticulate ceramic powders.
  • WO 02/42201 a process for the preparation of nanoparticulate metal oxides is described in which dissolved metal salts are thermally decomposed in the presence of surfactants.
  • the decomposition takes place under conditions under which the surfactants micelles, in addition, depending on the selected metal salt may require temperatures of several hundred degrees Celsius to achieve the decomposition.
  • the process is therefore very complex in terms of apparatus and energy.
  • WO 2004/052327 describes surface-modified nanoparticulate zinc oxides in which the surface modification comprises a coating with an organic see acid includes.
  • DE-A 10 2004 020 766 discloses surface-modified nanoparticulate metal oxides which have been prepared in the presence of polyaspartic acid.
  • EP 1455737 describes surface-modified nanoparticulate zinc oxides in which the surface modification comprises a coating with an oligo- or polyethylene glycol acid.
  • WO 98/13016 describes the use of surface-treated zinc oxide in cosmetic sunscreen preparations, wherein a surface treatment with polyacrylates is also disclosed. Data on the preparation of a treated with polyacrylates zinc oxide are not found.
  • a further object of the invention was to provide aqueous suspensions of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide and the development of methods for their use.
  • This object is achieved by surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide which are precipitated from a solution in the presence of a polyacrylate.
  • the invention thus provides a process for preparing surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, nickel disgust, copper, titanium, zinc and zirconium, comprising the steps
  • the metal oxide, metal hydroxide and metal oxide hydroxide may be both the anhydrous compounds and the corresponding hydrates.
  • the metal salts in process step a) may be metal halides, acetates, sulfates or nitrates.
  • Preferred metal salts are halides, for example zinc chloride or titanium tetrachloride, acetates, for example zinc acetate and nitrates, for example zinc nitrate.
  • a particularly preferred metal salt is zinc chloride or zinc nitrate.
  • the concentration of the metal salts in the solution 1 is generally in the range of 0.05 to 1 mol / l, preferably in the range of 0.1 to 0.5 mol / l, particularly preferably 0.2 to 0.4 mol / l
  • the strong bases to be used according to the invention may generally be any substances capable of having a pH in aqueous solution of from about 8 to about 13, preferably from about 9 to about 12.5, depending on their concentration produce. These may be, for example, metal oxides or hydroxides as well as ammonia or amines. Preference is given to using alkali metal hydroxides such as sodium or potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide or ammonia. More preferably, sodium hydroxide, potassium hydroxide and ammonia are used. In a preferred embodiment of the invention, ammonia can also be formed by thermal decomposition of urea in situ during process steps a) and / or b).
  • the concentration of the strong base in the solution 2 prepared in process step a) is generally selected so that in the solution 2 a Hydroxylionenkon- concentration in the range of 0.1 to 2 mol / l, preferably from 0.2 to 1 mol / l and more preferably from 0.4 to 0.8 mol / l.
  • c is a concentration and M n + is at least one metal ion of valency n.
  • M n + is at least one metal ion of valency n.
  • a solution 1 with a concentration of divalent metal ions of 0.2 mol / l preferably a solution 2 having a hydroxyl ion concentration of 0.4 mol / l is used.
  • the polyacrylates are polymers based on at least one ⁇ , ⁇ -unsaturated carboxylic acid, for example acrylic acid, methacrylic acid, dimethacrylic acid, ethacrylic acid, maleic acid, citraconic acid, methylenemalonic acid, crotonic acid, isocrotonic acid, fumaric acid, mesaconic acid and itaconic acid.
  • polyacrylates based on acrylic acid, methacrylic acid, maleic acid or mixtures thereof are used.
  • the proportion of the at least one ⁇ , ⁇ -unsaturated carboxylic acid in the polyacrylates is generally between 20 and 100 mol%, preferably between 50 and 100 mol%, particularly preferably between 75 and 100 mol%.
  • the polyacrylates to be used according to the invention can be used both in the form of the free acid and partially or completely neutralized in the form of their alkali metal, alkaline earth metal or ammonium salts. But they can also be used as salts of the respective polyacrylic acid and triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine, diethylenetriamine or tetraethylenepentamine.
  • the polyacrylates may contain other comonomers which are polymerized into the polymer chain, for example, the esters, amides and nitriles of the above carboxylic acids, eg.
  • Suitable as further copolymerizable comonomers are allylacetic acid, vinylacetic acid, acrylamidoglycolic acid, vinylsulphonic acid, allylsulphonic acid, methallylsulphonic acid, styrenesulphonic acid, acrylic acid (3-sulphopropyl) ester, methacrylic acid (3 sulfopropyl) ester or acrylamidomethylpropanesulfonic acid and phosphonic acid group-containing monomers such as vinylphosphonic acid, allylphosphonic acid or acrylamidomethanepropanephosphonic acid.
  • the monomers containing acid groups can be used in the polymerization in the form of the free acid groups and in partially or completely neutralized with bases form.
  • copolymerizable compounds are N-vinylcaprolactam, N-vinylimidazole, N-vinyl-2-methylimidazole, N-vinyl-4-methylimidazole, vinyl acetate, vinylpropionate, isobutene or styrene, and also compounds having more than one polymerizable double bond, for example diallyl ammonium chloride, ethylene glycol di methacrylate, diethylene glycol diacrylate, allyl methacrylate, trimethylolpropane triacrylate, tri allyl amine, tetraallyloxyethane, triallyl cyanurate, diallyl maleate, Tetraallylethy- diamine, Divinylidenharnstoff, pentaerythritol, pentaerythritol tri- and tetraallyl pentaerythritol, N, N-methylenebisacrylamide or N, N '- methylenebismethacrylamide.
  • mixtures of said comonomers are suitable for the preparation of the polyacrylates according to the invention.
  • mixtures of 50 to 100 mol% of acrylic acid and 0 to 50 mol% of one or more of the comonomers mentioned are suitable for the preparation of the polyacrylates according to the invention.
  • polyacrylates are under the brand name Sokalan ® (Fa. BASF Aktiengesellschaft) are commercially available.
  • the concentration of the polyacrylates in the solutions 1 and / or 2 prepared in process step a) is generally in the range from 0.1 to 20 g / l, preferably from 1 to 10 g / l, particularly preferably from 1.5 to 5 g / l.
  • the polyacrylates to be used according to the invention must have a corresponding water solubility.
  • the molecular weight of the polyacrylates to be used according to the invention is generally in the range from 800 to 250,000 g / mol, preferably in the range from 1000 to 100,000 g / mol, more preferably in the range from 1,000 to 20,000 g / mol.
  • a preferred embodiment of the process according to the invention is characterized in that the precipitation of the metal oxide, metal hydroxide and / or the metal oxide hydroxide takes place in the presence of a polyacrylate which is obtained from pure acrylic acid.
  • Sokalan ® PA 15 (Fa. BASF Aktiengesellschaft), the sodium salt of a polyacrylic acid is used.
  • the mixing of the two solutions 1 and 2 (aqueous metal salt solution and aqueous base solution) in process step b) takes place at a temperature in the range of 0 ° C. to 120 0 C, preferably in the range of 10 0 C to 100 ° C, particularly preferably in the range of 15 ° C to 80 ° C.
  • mixing may be carried out at a pH in the range of 3 to 13.
  • the pH during mixing is in the range of 8 to 13.
  • the time for the mixing of the two solutions in process step b) according to the invention is in the range of 1 second to 6 hours, preferably in the range of 1 minute to 2 hours. In general, the mixing time is longer with discontinuous driving than with continuous driving.
  • the mixing in process step b) can be carried out, for example, by combining an aqueous solution of a metal salt, for example zinc chloride or zinc nitrate, with an aqueous solution of a mixture of a polyacrylate and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide.
  • a metal salt for example zinc chloride or zinc nitrate
  • an aqueous solution of a mixture of a polyacrylate and a metal salt for example of zinc chloride or zinc nitrate
  • an alkali metal hydroxide or ammonium hydroxide in particular of sodium hydroxide
  • an aqueous solution of a mixture of a polyacrylate and a metal salt for example of zinc chloride or zinc nitrate
  • an aqueous solution of a mixture of a polyacrylate and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide are combined.
  • the mixing in step b) by addition of an aqueous solution of a mixture of a polyacrylate and an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide, to an aqueous solution of a metal salt, such as zinc chloride or zinc nitrate, or by addition of an aqueous Solution of an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide, to an aqueous solution of a mixture of a polyacrylate and a metal salt, for example zinc chloride or zinc nitrate.
  • a metal salt such as zinc chloride or zinc nitrate
  • an aqueous Solution of an alkali metal hydroxide or ammonium hydroxide, in particular sodium hydroxide to an aqueous solution of a mixture of a polyacrylate and a metal salt, for example zinc chloride or zinc nitrate.
  • the surface-modified nanoparticulate particles are formed, which precipitate out of the solution to form an aqueous suspension.
  • the mixing is carried out while stirring the mixture.
  • the stirring is preferably continued for a time between 30 minutes and 5 hours at a temperature in the range of 0 0 C to 120 0 C.
  • a further preferred embodiment of the method according to the invention is characterized in that at least one of the method steps a) to d) are carried out continuously. In continuous operation, the process step b) is preferably carried out in a tubular reactor.
  • the continuous process is carried out in the form that the mixing in step b) takes place in a first reaction space at a temperature T1 in which an aqueous solution 1 of at least one metal salt and an aqueous solution 2 of at least one strong base are introduced continuously at least one of the two solutions 1 and 2 contains at least one polyacrylate, from which the suspension formed is continuously withdrawn and transferred to a second reaction space for temperature control at a temperature T2, wherein the surface-modified nanoparticulate particles form.
  • the continuous process is carried out in the form that the temperature T2 is higher than the temperature T1.
  • the processes described in the introduction are particularly suitable for the preparation of surface-modified nanoparticulate particles of titanium dioxide and zinc oxide, in particular of zinc oxide.
  • the precipitation of the surface-modified nanoparticulate particles of zinc oxide from an aqueous solution of zinc acetate, zinc chloride or zinc nitrate takes place at a pH in the range of 8 to 13 in the presence of at least one polyacrylate.
  • an advantageous embodiment of the process according to the invention is characterized in that the surface-modified nanoparticulate particles of a metal oxide, metal hydroxide and / or metal oxide hydroxide, in particular of zinc oxide, have high light transmittance in the visible light range and low transmittance near ultraviolet light (UV-A). exhibit.
  • the ratio of the logarithm of the percent transmission (T) at a wavelength of 360 nm and the logarithm of the percent transmission at a wavelength of 450 nm [In T (360 nm) / ln T (450 nm)] is at least 15 , more preferably at least 18. This ratio is usually measured on a 5 to 10 wt .-% oil dispersion of the nanoparticulate particles (see US 6171580).
  • a further advantageous embodiment of the method according to the invention is characterized in that the surface-modified nanoparticulate particles of a metal oxide, metal hydroxide and / or metal oxide hydroxide, in particular of zinc oxide, a BET surface area in the range of 25 to 500 m 2 / g, preferably 30 to 400 m 2 / g, more preferably 40 to 300 m 2 / g.
  • the invention is based on the finding that, by surface modification of nanoparticulate metal oxides, metal hydroxides and / or metal oxide hydroxides with polyacrylates, long-term stability of dispersions of the surface-modified nanoparticulate metal oxides, in particular in cosmetic preparations, without undesirable changes in the pH during storage of these preparations can be achieved.
  • the separation of the precipitated particles from the aqueous suspension in process step c) can be carried out in a manner known per se, for example by filtration or centrifugation. If necessary, prior to isolation of the precipitated particles, the aqueous dispersion may be concentrated by means of a membrane process such as nano, ultra, micro or crossflow filtration and optionally at least partially freed of undesirable water soluble components, for example alkali metal salts such as sodium chloride or sodium nitrate.
  • a membrane process such as nano, ultra, micro or crossflow filtration and optionally at least partially freed of undesirable water soluble components, for example alkali metal salts such as sodium chloride or sodium nitrate.
  • step b) It has proved to be advantageous to carry out the separation of the surface-modified nanoparticulate particles from the aqueous suspension obtained in step b) at a temperature in the range from 10 to 50 ° C., preferably at room temperature. It is therefore advantageous to cool the aqueous suspension obtained in step b) to such a temperature, if appropriate.
  • the resulting filter cake can be dried in a conventional manner, for example in a drying oven at temperatures between 40 and 100 0 C, preferably between 50 and 80 0 C under atmospheric pressure tosureskon- stance.
  • a further subject of the present invention are surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, Nickel, copper, titanium, zinc and zirconium, and the surface modification comprises a coating with at least one polyacrylate, having a BET surface area in the range of 25 to 500 m 2 / g, preferably 30 to 400 m 2 / g, particularly preferably 40 to 300 m 2 / g, which are obtainable by the method described above.
  • the surface-modified nanoparticulate particles have a diameter of from 10 to 200 nm. This is particularly advantageous since a good re-dispersibility is ensured within this size distribution.
  • the surface-modified nanoparticulate particles have a diameter of 20 to 100 nm. This size range is particularly advantageous because, for example, after redispersion of such zinc oxide nanoparticles, the resulting suspensions are transparent and thus do not affect the color when added to cosmetic formulations. In addition, this results in the possibility for use in transparent films.
  • the nanoparticulate particles according to the invention are distinguished by a high light transmittance in the visible light range and by a low light transmittance in the region of the near ultraviolet light (UV-A).
  • the ratio of the logarithm of the percent transmission (T) at a wavelength of 360 nm and the logarithm of the percent transmission at a wavelength of 450 nm [In T (360 nm) / ln T (450 nm)] is at least 15 , more preferably at least 18.
  • Another object of the present invention is the use of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide, in particular titanium dioxide or zinc oxide, which are prepared by the process according to the invention, as UV protectants in cosmetic sunscreen preparations, as a stabilizer in plastics and as an antimicrobial agent.
  • the surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, in particular titanium dioxide or zinc oxide are redispersible in a liquid medium and form stable suspensions.
  • the suspensions prepared from the zinc oxide according to the invention need not be redispersed before further processing, but can be processed directly.
  • the surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide are redispersible in polar organic solvents and form stable suspensions. This is particularly advantageous, since this uniform incorporation, for example, in plastics or films is possible.
  • the surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide are redispersible in water and form stable suspensions there. This is particularly advantageous since it opens up the possibility of using the material according to the invention, for example in cosmetic formulations, whereby the avoidance of organic solvents is a great advantage. provides. Also conceivable are mixtures of water and polar organic solvents.
  • the surface-modified nanoparticulate particles according to the invention of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide require their use in the form of an aqueous suspension, their isolation as a solid may optionally be dispensed with.
  • Another object of the present invention is therefore a process for preparing an aqueous suspension of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, Iron, manganese, cobalt, nickel, copper, titanium, zinc and zirconium, comprising the steps
  • solution 1 preparation of a solution of water and at least one metal salt of the abovementioned metals (solution 1) and a solution of water and at least one strong base (solution 2), at least one of the two solutions 1 and 2 containing at least one polyacrylate,
  • step b) mixing the solutions 1 and 2 prepared in step a) at a temperature in the range from 0 to 120 ° C., the surface-modified nanoparticulate particles forming and precipitating out of the solution to form an aqueous suspension,
  • the aqueous suspension formed in step b) can be concentrated in process step c), for example if a higher solids content is desired.
  • the concentration can be carried out in a manner known per se, for example by distilling off the water (at atmospheric pressure or at reduced pressure), filtering or centrifuging.
  • Suitable by-products are, first and foremost, salts dissolved in water, which in the case of the present invention Reaction between the metal salt and the strong base besides the desired metal oxide, metal hydroxide and / or metal oxide hydroxide particles are formed, for example sodium chloride, sodium nitrate or ammonium chloride.
  • salts dissolved in water which in the case of the present invention Reaction between the metal salt and the strong base besides the desired metal oxide, metal hydroxide and / or metal oxide hydroxide particles are formed, for example sodium chloride, sodium nitrate or ammonium chloride.
  • Such by-products can be largely removed from the aqueous suspension, for example by means of a membrane process such as nano-, ultra-, micro- or crossflow filtration.
  • a further preferred embodiment of the method according to the invention is characterized in that at least one of the method steps a) to c) are carried out continuously.
  • a further subject of the present invention are aqueous suspensions of surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide hydroxide, wherein the metal or metals are selected from the group consisting of aluminum, magnesium, cerium, iron, manganese, cobalt, Nickel, copper, titanium, zinc and zirconium, and the surface modification comprises a coating with at least one polyacrylate obtainable by the method described above.
  • the surface-modified nanoparticulate particles in the aqueous suspensions are coated with a polyacrylate which is a polyacrylic acid.
  • Another object of the present invention is the use of aqueous suspensions surface-modified nanoparticulate particles of at least one metal oxide, metal hydroxide and / or metal oxide, in particular titanium dioxide or zinc oxide, which are prepared by the process according to the invention, as UV protectants in cosmetic sunscreen preparations, as a stabilizer in plastics or as an antimicrobial agent.
  • Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l.
  • the solution 2 contained 32 g of sodium hydroxide per liter and thus had a Hydroxylio- nenkonzentration of 0.8 mol / l.
  • the solution contained 2 4 g / l of Sokalan ® PA 15th
  • a suspension flow of 0.96 l / min was pumped out of the glass reactor via a riser pipe by means of a gear pump (Gather Industrie GmbH, D-40822 Mettmann) and within a minute to a temperature of 85 ° in a downstream heat exchanger C heated.
  • the suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds. Thereafter, the suspension successively passed through a third and fourth heat exchanger, in which the suspension was cooled to room temperature within a further minute.
  • the freshly prepared suspension was thickened by the factor 15 in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD). Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sigma 3K30, 20,000 rpm, 40.700g) with subsequent drying at 50 0 C.
  • the resulting powder In the UV-VIS spectrum, the resulting powder exhibited the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. From the half-width of the X-ray reflections, a crystallite size was calculated, which see 16 nm [for the (102) reflection] and 57 nm [for the (002) reflection]. In the transmission electron microscopy (TEM), the powder obtained had an average particle size of about 50.
  • TEM transmission electron microscopy
  • Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l.
  • the solution 2 contained 32 g of sodium hydroxide per liter and thus had a Hydroxylio- nenkonzentration of 0.8 mol / l. Furthermore, the solution 2 still contained 4 g / l of Sokalan ® PA 18 PN.
  • a suspension flow of 0.96 l / min was pumped out of the glass reactor via a riser pipe by means of a gear pump (Gather Industrie GmbH, D-40822 Mettmann) and within a minute to a temperature of 85 ° in a downstream heat exchanger C heated.
  • the suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds.
  • the suspension subsequently passed through a third and fourth heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.
  • the freshly prepared suspension was thickened by the factor 15 in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD). Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sigma 3K30, 20,000 rpm, 40.700g) with subsequent drying at 50 0 C.
  • the resulting powder In the UV-VIS spectrum, the resulting powder exhibited the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. In By transmission electron microscopy (TEM), the resulting powder had an average particle size of about 50 nm.
  • TEM transmission electron microscopy
  • Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l.
  • the solution 2 contained 32 g of sodium hydroxide per liter and thus had a Hydroxylio- nenkonzentration of 0.8 mol / l.
  • the solution contained 2 4 g / l of Sokalan ® PA 20th
  • the suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds.
  • the suspension subsequently passed through a third and fourth heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.
  • the freshly prepared suspension was thickened by a factor of 15 in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD). Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sigma 3K30, 20,000 rpm, 40.700g) with subsequent drying at 50 0 C.
  • the powder obtained had the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. In the transmission electron microscopy (TEM), the powder obtained had an average particle size of about 70 nm.
  • Solution 1 contained 54.52 g zinc chloride per liter and had a zinc ion concentration of 0.4 mol / l.
  • the solution 2 contained 32 g of sodium hydroxide per liter and thus had a Hydroxylio- nenkonzentration of 0.8 mol / l. Furthermore, the solution 2 still contained 4 g / l of Sokalan ® PA 30 PN.
  • a suspension flow of 0.96 l / min was pumped out of the glass reactor via a riser pipe by means of a gear pump (Gather Industrie GmbH, D-40822 Mettmann) and within a minute to a temperature of 85 ° in a downstream heat exchanger C heated.
  • the suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds.
  • the suspension subsequently passed through a third and fourth heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.
  • the freshly prepared suspension was thickened by the factor 15 in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD). Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sigma 3K30, 20,000 rpm, 40.700g) with subsequent drying at 50 0 C.
  • the resulting powder In the UV-VIS spectrum, the resulting powder exhibited the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. In the transmission electron microscopy (TEM), the powder obtained had an average particle size of about 80 nm.
  • Solution 1 contained 27.26 g of zinc chloride per liter and had a zinc ion concentration of 0.2 mol / l.
  • Solution 2 contained 16 g of sodium hydroxide per liter and thus had a hydroxyl ion concentration of 0.4 mol / l. Furthermore, the solution 2 still contained 4 g / l of Sokalan ® PA 30 PN.
  • the suspension obtained then passed through a second heat exchanger, in which the suspension was kept at 85 ° C. for a further 30 seconds.
  • the suspension subsequently passed through a third and fourth heat exchanger in succession, in which the suspension was cooled to room temperature within a further minute.
  • the freshly prepared suspension was thickened by a factor of 15 in a crossflow ultrafiltration laboratory system (Sartorius, type SF Alpha, PES cassette, cut off 100 kD). Subsequent isolation of the solid powder was carried out using an ultracentrifuge (Sigma 3K30, 20,000 rpm, 40.700g) with subsequent drying at 50 0 C.
  • the powder obtained had the absorption band characteristic of zinc oxide at about 350-360 nm. In line with this, the X-ray diffraction of the powder showed only the diffraction reflections of hexagonal zinc oxide. In transmission electron microscopy (TEM), the powder obtained had an average particle size of about 40 nm.

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Abstract

La présente invention concerne un procédé de fabrication de nanoparticules modifiées en surface d'au moins un oxyde métallique, un hydroxyde métallique et/ou un oxyde-hydroxyde métallique, ainsi que de suspensions aqueuses de ces particules. En outre, l'invention concerne les nanoparticules modifiées en surface, pouvant être obtenues par ce procédé, d'au moins un oxyde métallique, un hydroxyde métallique et/ou un oxyde-hydroxyde métallique et des suspensions aqueuses de ces particules ainsi que leur utilisation pour des préparations cosmétiques antisolaires, comme stabilisant dans des matières plastiques et comme agent antimicrobien.
EP08717951A 2007-03-23 2008-03-18 Procédé de fabrication d'oxydes métalliques, hydroxydes métalliques et/ou oxydes-hydroxydes métalliques nanoparticulaires, modifiés en surface Withdrawn EP2129360A1 (fr)

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PCT/EP2008/053218 WO2008116790A1 (fr) 2007-03-23 2008-03-18 Procédé de fabrication d'oxydes métalliques, hydroxydes métalliques et/ou oxydes-hydroxydes métalliques nanoparticulaires, modifiés en surface
EP08717951A EP2129360A1 (fr) 2007-03-23 2008-03-18 Procédé de fabrication d'oxydes métalliques, hydroxydes métalliques et/ou oxydes-hydroxydes métalliques nanoparticulaires, modifiés en surface

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KR101455887B1 (ko) 2014-11-03
CN101641077B (zh) 2013-01-16
AU2008231831A1 (en) 2008-10-02
CN101641077A (zh) 2010-02-03
BRPI0809159A2 (pt) 2014-09-16
JP2010521411A (ja) 2010-06-24
CA2681153A1 (fr) 2008-10-02
KR20090125194A (ko) 2009-12-03
US20100119829A1 (en) 2010-05-13
JP5393652B2 (ja) 2014-01-22
BRPI0809159B1 (pt) 2016-06-07
WO2008116790A1 (fr) 2008-10-02

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