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EP1922369A1 - Nanoparticules a surface modifiee, constituees par un oxyde d'aluminium et des oxydes d'elements du i. ou ii. groupe principal de la classification periodique des elements et realisation associee - Google Patents

Nanoparticules a surface modifiee, constituees par un oxyde d'aluminium et des oxydes d'elements du i. ou ii. groupe principal de la classification periodique des elements et realisation associee

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Publication number
EP1922369A1
EP1922369A1 EP06776873A EP06776873A EP1922369A1 EP 1922369 A1 EP1922369 A1 EP 1922369A1 EP 06776873 A EP06776873 A EP 06776873A EP 06776873 A EP06776873 A EP 06776873A EP 1922369 A1 EP1922369 A1 EP 1922369A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
agglomerates
oxides
modified
modified nanoparticles
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Withdrawn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
EP06776873A
Other languages
German (de)
English (en)
Inventor
Norbert RÖSCH
Ernst Krendlinger
Anja Heinze
Karl Zeisberger
Peter Klug
Waltraud Simsch
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.)
Archroma IP GmbH
Original Assignee
Clariant International Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from DE102005039435A external-priority patent/DE102005039435A1/de
Priority claimed from DE102005039436A external-priority patent/DE102005039436B4/de
Priority claimed from DE102006012319A external-priority patent/DE102006012319A1/de
Priority claimed from DE200610020516 external-priority patent/DE102006020516A1/de
Application filed by Clariant International Ltd filed Critical Clariant International Ltd
Publication of EP1922369A1 publication Critical patent/EP1922369A1/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Withdrawn legal-status Critical Current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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00—Compounds of aluminium
    • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/021—After-treatment of oxides or hydroxides
    • C01F7/023—Grinding, deagglomeration or disintegration
    • 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
    • C09C3/04—Physical treatment, e.g. grinding, treatment with ultrasonic vibrations
    • C09C3/041—Grinding
    • 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
    • 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
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/50—Solid solutions
    • C01P2002/52—Solid solutions containing elements as dopants
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • 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
    • 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
    • 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.]
    • Y10T428/2995—Silane, siloxane or silicone coating

Definitions

  • the present invention relates to surface-modified nanoparticles, and their preparation, wherein the nanoparticles consist of Al 2 O 3 with fractions of oxides of the elements of the I. and II. Main group of the Periodic Table.
  • Fine alumina powders are used in particular for ceramic applications, for matrix reinforcement of organic or metallic layers, as fillers, polishing powders, for the production of abrasives, as additives in paints and laminates as well as for other special applications.
  • the alumina powders are often surface-modified with silanes for better adaptation to the resin layers. Both the adhesion and the optical property are improved. This manifests itself in a decrease in turbidity.
  • silane-modified fumed alumina for use in toners (DE 42 02 694).
  • Nanoparticles of Al 2 O 3 whose surface is modified with silanes are described in WO 02/051376. In their preparation, one starts from a commercially available Al 2 O 3 , which is then treated with a silane. Production of the nanoparticles and their modification are thus carried out in two separate steps. Commercially available nanocorundum (0C-Al 2 O 3 ) is present as a powder. Due to the high surface energy, however, nanoparticles always accumulate to form larger agglomerates, so that in reality they are not true nanoparticles. Accordingly, the particles coated with silanes according to WO 02/051 376 are correspondingly large.
  • EP 1 123 354 (IOM Amsterdam) describes polymerisable metal oxide particles which are modified with various compounds which have a reactive, wear functional group. Suitable modifiable compounds include silanes.
  • the metal oxide particles here exclusively oxides of a metal or metalloid of the third to sixth main group, the first to eighth subgroup of the periodic table or the lanthanides are used, mixed oxides with a proportion of oxides of the first and second main groups are not described.
  • WO 2004/069400 (InM Saar Hampshiren) describes a process for the preparation of a functional colloid, in which particles are mechanically comminuted in a dispersant in the presence of a modifier, so that the modifier is at least partially chemically bound to the comminuted colloid particles. This method is based on homogeneous particles, the deagglomeration of agglomerates from existing nanoparticles is not disclosed.
  • No. 6,896,958 B1 (nanophase) describes a process in which nanocrystalline substances from the group of ceramic or metallic substances are dispersed in a solvent and treated with siloxanes. The resulting dispersions are used in crosslinkable resins to improve the scratch resistance.
  • surface-modified nanoparticles in the form of mixed oxides of Al 2 O 3 containing oxides of elements from the first and second main groups of the Periodic Table, are particularly easy to produce by deagglomeration of agglomerates of these mixed oxides in a solvent with the addition of a coating agent to let.
  • the coating agents used are preferably silanes or siloxanes.
  • the invention relates to surface-modified nanoparticles consisting of 50-99.9% by weight of aluminum oxide and 0.1-50% by weight of oxides of elements of the 1st or 2nd main group of the Periodic Table, these nanoparticles having a coating agent on the surface are modified.
  • the alumina in these mixed oxides is preferably present for the most part in the rhombohedral ⁇ -modification (corundum).
  • the mixed oxides according to the present invention preferably have a crystal it size of less than 1 micron, preferably less than 0.2 microns and more preferably between 0.001 and 0.09 microns. Particles of this size according to the invention will be referred to below as mixed oxide nanoparticles.
  • the mixed oxide nanoparticles according to the invention can be prepared by different processes described below. These process descriptions refer to the production of pure alumina particles, but it goes without saying that in all these process variants in addition to Al-containing starting compounds and those compounds from elements of the I. or II. Main group of the Periodic Table must be present to form the mixed oxides according to the invention. For this purpose, especially the chlorides, but also the oxides, oxychlorides, carbonates, sulfates or other suitable salts come into question. The amount of such oxide formers is such that the finished nanoparticles contain the aforementioned amounts of oxide MeO.
  • agglomerates of these mixed oxides are used, which are then deagglomerated to the desired particle size.
  • These agglomerates can be prepared by methods described below.
  • Such agglomerates can be prepared, for example, by various chemical syntheses. These are usually precipitation reactions (hydroxide precipitation, hydrolysis of organometallic compounds) with subsequent calcination. Crystallization seeds are often added to reduce the transition temperature to the ⁇ -alumina. The sols thus obtained are dried and thereby converted into a gel. The further calcination then takes place at temperatures between 350 0 C and 650 0 C. For the conversion to Ct-Al 2 O 3 must then be annealed at temperatures around 1000 0 C. The processes are described in detail in DE 199 22 492. Another way is the aerosol process. The desired molecules are obtained from chemical reactions of a Precursorgases or by rapid cooling of a supersaturated gas.
  • the formation of the particles occurs either through collision or the constant equilibrium evaporation and condensation of molecular clusters.
  • the newly formed particles grow by further collision with product molecules (condensation) and / or particles (coagulation). If the coagulation rate is greater than that of the new growth or growth, agglomerates of spherical primary particles are formed.
  • Nanoparticles are formed here by the decomposition of Precursormolekülen in the flame at 1500 0 C - 2500 0 C.
  • AICb So far only the corresponding clay could be produced.
  • Flame reactors are now used industrially for the synthesis of submicroparticles such as carbon black, pigment Ti ⁇ 2, silica and alumina.
  • Small particles can also be formed from drops with the help of centrifugal force, compressed air, sound, ultrasound and other methods.
  • the drops are then converted into powder by direct pyrolysis or by in situ reactions with other gases.
  • the spray and freeze drying should be mentioned.
  • precursor drops are transported through a high temperature field (flame, oven), resulting in rapid evaporation of the volatile component or initiating the decomposition reaction to the desired product.
  • the desired particles are collected in filters.
  • the production of BaTiO 3 from an aqueous solution of barium acetate and titanium lactate can be mentioned here.
  • the nanoparticles must be released. This is preferably done by grinding or by treatment with ultrasound. According to the invention, this deagglomeration takes place in the presence of a
  • Solvent and a coating agent preferably a silane, which saturates the resulting active and reactive surfaces by a chemical reaction or physical attachment during the milling process and thus prevents reagglomeration.
  • the nano-mixed oxide remains as a small particle. It is also possible to add the coating agent after deagglomeration.
  • agglomerates are used which, as described in Ber. DKG 74 (1997) no. 11/12, pp. 719-722, as previously described.
  • the starting point here is aluminum chlorohydrate, which has the formula Al 2 (OH) x Cl y , where x is a number from 2.5 to 5.5 and y is a number from 3.5 to 0.5 and the sum of x and y always 6.
  • This aluminum chlorohydrate is mixed with crystallization seeds as an aqueous solution, then dried and then subjected to a thermal treatment (calcination). Preference is given to starting from about 50% aqueous solutions, as they are commercially available.
  • Such a solution is mixed with nuclei which promote the formation of the ⁇ -modification of Al 2 O 3 . In particular, such nuclei cause a lowering of the temperature for the formation of the ⁇ -modification in the subsequent thermal treatment.
  • germs are preferably in question finely disperse corundum, diaspore or hematite. Particular preference is given to taking very finely divided ⁇ -Al 2 O 3 nuclei having an average particle size of less than 0.1 ⁇ m. In general, 2 to 3 wt .-% of germs based on the resulting alumina from.
  • This starting solution additionally contains oxide formers in order to produce the oxides MeO in the mixed oxide.
  • oxide formers especially the chlorides of the elements of the I. and II. Main group of the Periodic Table, in particular the chlorides of the elements Ca and Mg, but also other soluble or dispersible salts such as oxides, oxychlorides, carbonates or sulfates.
  • the amount of oxide generator is such that the finished nanoparticles contain 0.01 to 50% by weight of the oxide MeO.
  • the oxides of I. and II. Main group may be present as a separate phase in addition to the alumina or with this real mixed oxides such. Form spinels etc.
  • the term "mixed oxides" in the context of this invention should be understood to include both types.
  • This suspension of aluminum chlorohydrate, germs and oxide formers is then evaporated to dryness and subjected to a thermal treatment (calcination).
  • This calcination is carried out in suitable devices, for example in push-through, chamber, tube, rotary kiln or microwave ovens or in a fluidized bed reactor.
  • suitable devices for example in push-through, chamber, tube, rotary kiln or microwave ovens or in a fluidized bed reactor.
  • the temperature for the calcination should not exceed 1400 0 C.
  • the lower temperature limit depends on the desired yield of nanocrystalline mixed oxide, the desired residual chlorine content and the content of Germinate.
  • the formation of the nanoparticles begins at about 500 0 C, but to keep the chlorine content low and the yield of nanoparticles high, but you will work preferably at 700 to 1100 0 C, in particular at 1000 to 1100 0 C.
  • agglomerates accumulate in the form of nearly spherical nanoparticles. These particles consist of Al 2 O 3 and MeO. The content of MeO acts as an inhibitor of crystal growth and keeps the crystallite size small. As a result, the agglomerates, as obtained by the calcination described above, clearly differ from the particles used in the process described in WO 2004/069 400, which are coarser, inherently homogeneous particles and not agglomerates of pre-fabricated nanoparticles.
  • the agglomerates are preferably comminuted by wet grinding in a solvent, for example in an attritor mill, bead mill or stirred mill.
  • a solvent for example in an attritor mill, bead mill or stirred mill.
  • a suspension of nanoparticles with a d90 value of approximately 50 nm is obtained.
  • Another possibility for deagglomeration is sonication.
  • the deagglomeration in Make the presence of the coating agent, for example by adding the coating agent during grinding in the mill.
  • a second possibility consists of first destroying the agglomerates of the nanoparticles and then treating the nanoparticles, preferably in the form of a suspension in a solvent, with the coating agent.
  • Suitable solvents for deagglomeration are both water and customary solvents, preferably those which are also used in the paint industry, such as, for example, C 1 -C 4 -alcohols, in particular methanol, ethanol or isopropanol, acetone, tetrahydrofuran, butyl acetate.
  • an inorganic or organic acid such as HCl, HNO 3 , formic acid or acetic acid should be added to stabilize the resulting nanoparticles in the aqueous suspension.
  • the amount of acid may be 0.1 to 5 wt .-%, based on the mixed oxide.
  • aqueous suspension of the acid-modified nanoparticles is then preferably the grain fraction having a particle diameter of less than 20 nm separated by centrifugation.
  • the coating agent preferably a silane or siloxane
  • the nanoparticles thus treated precipitate are separated and dried to a powder, for example by freeze-drying.
  • Suitable coating agents are preferably silanes or siloxanes or mixtures thereof.
  • suitable coating agents are all substances which can bind physically to the surface of the mixed oxides (adsorption) or which can bond to form a chemical bond on the surface of the mixed oxide particles. Since the surface of the mixed oxide particles is hydrophilic and free hydroxy groups are available, suitable coating agents are alcohols, compounds having amino, hydroxyl, carbonyl, carboxyl or mercapto functions, silanes or siloxanes. Examples of such coating compositions are polyvinyl alcohol, mono-, di- and tricarboxylic acids, Amino acids, amines, waxes, surfactants, hydroxycarboxylic acids, organosilanes and organosiloxanes.
  • Suitable silanes or siloxanes are compounds of the formulas
  • R, R ', R ", R 1 " identical or different from each other, an alkyl radical having 1-18 C atoms or a phenyl radical or an alkylphenyl or a phenylalkyl radical having 6 - 18 C-atoms or a radical of the general formula - ( C m H 2m -O) pC q H 2 q + i or a radical of the general formula -C 3 H 2s Y or a radical of the general formula -XZn,
  • n is an integer meaning 1 ⁇ n ⁇ 1000, preferably 1 ⁇ n ⁇ 100
  • m is an integer 0 ⁇ m ⁇ 12
  • p is an integer 0 ⁇ p ⁇ 60
  • q is an integer 0 ⁇ q ⁇ 40
  • r is an integer 2 ⁇ r ⁇ 10 and s is an integer 0 ⁇ s ⁇ 18 and
  • Y is a reactive group, for example ⁇ , ⁇ -ethylenically unsaturated groups, such as (meth) acryloyl, vinyl or allyl groups, amino, amido, ureido, hydroxyl, epoxy, isocyanato, mercapto, sulfonyl, Phosphonyl, trialkoxylsilyl, alkyldialkoxysilyl, dialkylmonoalkoxysilyl, anhydride and / or carboxyl groups, imido, imino, sulfite, sulfate, sulfonate, phosphine, phosphite, phosphate, phosphonate groups, and X is a t-functional Oligomer with t an integer 2 ⁇ t ⁇ 8 and Z in turn a remainder
  • R [-Si (R 1 R 11 KH n Si (R 1 R 11 JR 1 ”) or cyclo - [-Si (R'R") - O-] r Si (R 1 R 11 JO- represents as defined above.
  • the t-functional oligomer X is preferably selected from:
  • radicals of oligoethers are compounds of the type - (C a H 2a -O) b - C a H 2a - or O- (C a H2a-O) b -CaH 2a -O with 2 ⁇ a ⁇ 12 and 1 ⁇ b ⁇ 60, z.
  • residues of oligoesters are compounds of the type -C b H 2b - (C (CO) C a H 2 a- (CO) O- C b H 2b -) c- or -OC b H 2b - (C ( CO) C a H 2a - (CO) OC b H 2b -) c -O- with a and b different or equal to 3 ⁇ a ⁇ 12, 3 ⁇ b ⁇ 12 and 1 ⁇ c ⁇ 30, z.
  • silanes of the type defined above are, for. Hexamethyldisiloxane, octamethyltrisiloxane, other homologous and isomeric compounds of the series Si n O n-1 (CH 3 ) 2 n + 2, where n is an integer 2 ⁇ n ⁇ 1000, e.g. B. Polydimethylsiloxane 200® fluid (2O cSt).
  • ⁇ -OH groups are also the corresponding difunctional compounds with epoxy, isocyanato, vinyl, AIIyI- and di (meth) acryloyl used, for.
  • R is an alkyl, such as. For example, methyl, ethyl, n-propyl, i-propyl, butyl n 1 to 20.
  • R is an alkyl, such as. Methyl, ethyl, n-propyl, i-propyl, butyl,
  • R 1 is an alkyl, such as. Methyl, ethyl, n-propyl, i-propyl, butyl,
  • R ' is a cycloalkyl n is an integer from 1 - 20 x + y 3 x 1 or 2 y 1 or 2 1 O
  • Preferred silanes are the silanes listed below: triethoxysilane, octadecyltimethoxysilane, 3- (trimethoxysilyl) -propylmethacrylate, 3- (trimethoxysilyl) -propylacrylate, 3- (trimethoxysilyl) -methylmethacrylate, 3- (trimethoxysilyl) -methylacrylate, 3- (trimethoxysilyl) ethylmethacrylate, 3- (trimethoxysilyl) -ethylacrylate, 3- (trimethoxysilyl) -pentylmethacrylate, 3- (trimethoxysilyl) -pentylacrylate, 3- (trimethoxysilyl) -hexylmethacrylate, 3- (trimethoxysilyl) -hexylacrylate, 3- (trimethoxysilyl) -butylmethacrylate , 3- (trimeth
  • Tetramethoxysilanes Tetramethoxysilanes, tetraethoxysilanes, oligomeric tetraethoxysilanes (DYNASIL® 40 from Degussa), tetra-n-propoxysilanes, 3-glycidyloxypropyltrimethoxysilanes, 3-glycidyloxypropyltriethoxysilanes, 3-methacryloxypropyltrimethoxysilanes, vinyltrimethoxysilanes, vinyltriethoxysilanes, 3-mercaptopropyltrimethoxysilanes,
  • 3-aminopropyltriethoxysilanes 3-aminopropyltrimethoxysilanes, 2-aminoethyl-3-aminopropyltrimethoxysilanes, triaminofunctional propyltrimethoxysilanes (DYN AS YLAN® TRIAMINO from Degussa), N- (n-butyl-3-aminopropyltrimethoxysilanes, 3-aminopropylmethyldiethoxysilanes.
  • the coating compositions in particular the silanes or siloxanes, are preferably added in molar ratios of mixed oxide nanoparticles to silane of from 1: 1 to 10: 1.
  • the amount of solvent in the deagglomeration is generally 80 to 90 wt .-%, based on the total amount of mixed oxide nanoparticles and solvent.
  • the deagglomeration by grinding and simultaneous modification with the coating agent is preferably carried out at temperatures of 20 to 150 0 C, more preferably at 20 to 9O 0 C.
  • the suspension is subsequently separated from the grinding beads.
  • the suspension can be heated to complete the reaction for up to 30 hours. Finally, the solvent is distilled off and the remaining residue is dried. It may also be advantageous to leave the modified mixed oxide nanoparticles in the solvent and to use the dispersion for other applications.
  • the coating oxide-modified mixed oxide nanoparticles prepared in this way can be incorporated into transparent surface finishes or coatings, thereby achieving improved scratch protection. Modification with the coating agents allows the mixed oxide nanoparticles to be readily dispersed in non-aqueous systems. In addition, the coatings show less clouding compared to layers containing unmodified nanoparticles. Examples:
  • Magnesium chloride mixture was crushed in a mortar, resulting in a coarse powder.
  • the powder was calcined in a rotary kiln at 1050 0 C.
  • the contact time in the hot zone was a maximum of 5 min.
  • a white powder was obtained whose grain distribution corresponded to the feed material.
  • An X-ray structure analysis shows that predominantly ⁇ -alumina is present.
  • the images of the SEM image taken showed crystallites in the range 10 - 80 nm (estimate from SEM image), which are present as agglomerates.
  • the residual chlorine content was only a few ppm.
  • Zirconia (stabilized with yttrium) and had a size of 0.3 mm.
  • Example 1 40 g of the oxide mixture (MgO-doped corundum) from Example 1 was suspended in 160 g of methanol and deagglomerated in a vertical stirred ball mill from Netzsch (type PE 075). After 3 hours, the suspension was separated from the beads and transferred to a round bottom flask with reflux condenser. To the suspension was added 40 g of trimethoxy-octylsilane and heated at reflux for 2 h. After removal of the solvent, the coated oxide mixture was isolated and dried in a drying oven for another 20 h at 110 0 C. The product thus obtained is identical to the sample from Example 1.
  • the oxide mixture MgO-doped corundum
  • Example 2 40 g of the oxide mixture (MgO-doped corundum) from Example 1 was suspended in 160 g of methanol and deagglomerated in a vertical stirred ball mill from Netzsch (type PE 075). After 2 h, 20 g of 3- (trimethoxysilyl) propyl methacrylate (Dynasilan Memo, Degussa) were added and the suspension was deagglomerated in the stirred ball mill for a further 2 h. Subsequently, the suspension was separated from the beads and transferred to a round bottom flask with reflux condenser. Reflux was continued for an additional 2 hours before the solvent was distilled off.
  • the oxide mixture MgO-doped corundum
  • Example 2 40 g of the oxide mixture (MgO-doped corundum) from Example 1 was suspended in 160 g of methanol and deagglomerated in a vertical stirred ball mill from Netzsch (type PE 075). After 2 h, 20 g
  • Example 5 40 g of the oxide mixture (doped with MgO corundum) from Example 1 was suspended in 160 g of acetone and disagglomerated in a vertical stirred ball mill from. Netzsch (type PE 075). After 2 h, 20 g of aminopropyltrimethoxysilane (Dynasilan Ammo, Degussa) were added and the suspension was deagglomerated in the stirred ball mill for a further 2 h. Subsequently, the suspension was separated from the beads and transferred to a round bottom flask with reflux condenser. Reflux was continued for an additional 2 hours before the solvent was distilled off.
  • Example 5 40 g of the oxide mixture (doped with MgO corundum) from Example 1 was suspended in 160 g of acetone and disagglomerated in a vertical stirred ball mill from. Netzsch (type PE 075). After 2 h, 20 g of aminopropyltrimethoxysilane (Dyna
  • Example 2 40 g of the oxide mixture (doped with MgO corundum) from Example 1 was suspended in 160 g of acetone and disagglomerated in a vertical stirred ball mill from. Netzsch (type PE 075). After 2 h, 20 g of glycidyltrimethoxysilane (Dynasilan Glymo, Degussa) were added and the suspension was deagglomerated for a further 2 hours in the recycle ball mill. Subsequently, the suspension was separated from the beads and transferred to a round bottom flask with reflux condenser. Reflux was continued for an additional 2 hours before the solvent was distilled off.
  • glycidyltrimethoxysilane Dynasilan Glymo, Degussa
  • Example 2 40 g of the oxide mixture (MgO doped corundum) from Example 1 was suspended in 160 g of n-butanol and disagglomerated in a vertical stirred ball mill from Netzsch (type PE 075). After 2 h, a mixture of 5 g of aminopropyltrimethoxysilane (Dynasilan Glymo; Degussa) and 15 g of octyltriethoxysilane was added and the suspension was deagglomerated in the stirred ball mill for a further 2 h. The suspension remains stable for weeks without evidence of sedimentation of the coated mixed oxide.
  • the oxide mixture MgO doped corundum

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Abstract

L'invention concerne des nanoparticules d'oxyde mixte constituées par un oxyde d'aluminium et des oxydes d'éléments du I. ou II. groupe principal de la classification périodique des éléments. Ces nanoparticules d'oxyde mixte ont une surface modifiée par un agent d'enduction, de préférence un silane ou un siloxane.
EP06776873A 2005-08-18 2006-08-16 Nanoparticules a surface modifiee, constituees par un oxyde d'aluminium et des oxydes d'elements du i. ou ii. groupe principal de la classification periodique des elements et realisation associee Withdrawn EP1922369A1 (fr)

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DE102005039435A DE102005039435A1 (de) 2005-08-18 2005-08-18 Verfahren zur Herstellung von mit Silanen oberflächenmodifiziertem Nanokorund
DE102005039436A DE102005039436B4 (de) 2005-08-18 2005-08-18 Beschichtungsmassen enthaltend mit Silanen modifizierte Nanopartikel
DE102006012319A DE102006012319A1 (de) 2006-03-17 2006-03-17 Kosmetische Mittel enthaltend nanopartikuläres Korund
DE200610020516 DE102006020516A1 (de) 2006-04-29 2006-04-29 Oberflächenmodifizierte Nanopartikel aus Aluminiumoxid und Oxiden von Elementen der I. und II. Hauptgruppe des Periodensystems sowie deren Herstellung
PCT/EP2006/008067 WO2007020064A1 (fr) 2005-08-18 2006-08-16 Nanoparticules a surface modifiee, constituees par un oxyde d'aluminium et des oxydes d'elements du i. ou ii. groupe principal de la classification periodique des elements et realisation associee

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DE102005033393B4 (de) * 2005-07-16 2014-04-03 Clariant International Limited Verfahren zur Herstellung von nanokristallinem α-Al2O3
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DE102006032582A1 (de) * 2006-07-13 2008-01-24 Clariant International Limited Verfahren zur Herstellung von Nanopartikeln aus Aluminiumspinellen und deren Anwendung
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KR102605719B1 (ko) * 2020-12-23 2023-11-22 중앙대학교 산학협력단 볼밀링 공정을 이용한 무기물 입자의 표면 개질 방법 및 상기 방법으로 개질된 무기물 입자

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US20090226726A1 (en) 2009-09-10
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KR20080036156A (ko) 2008-04-24

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