EP2019848A1 - Nanoparticules - Google Patents

Nanoparticules

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Publication number
EP2019848A1
EP2019848A1 EP07724958A EP07724958A EP2019848A1 EP 2019848 A1 EP2019848 A1 EP 2019848A1 EP 07724958 A EP07724958 A EP 07724958A EP 07724958 A EP07724958 A EP 07724958A EP 2019848 A1 EP2019848 A1 EP 2019848A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
atoms
particles
organic solvent
polymer
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Withdrawn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
EP07724958A
Other languages
German (de)
English (en)
Inventor
Matthias Koch
Gerhard Jonschker
Sabine Renker
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
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Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP2019848A1 publication Critical patent/EP2019848A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • 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
    • 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
    • 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
    • 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
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • 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
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • 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
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter

Definitions

  • the invention relates to nanoparticles, in particular surface-modified nanoparticles, to a production method for such particles and to their use for UV protection.
  • inorganic nanoparticles inorganic nanoparticles in a polymer matrix can not only the mechanical properties, such. Impact resistance, of the matrix, but also changes their optical properties, e.g. wavelength-dependent transmission, color (absorption spectrum) and refractive index.
  • particle size plays an important role, since the addition of a substance with a refractive index which differs from the refractive index of the matrix, inevitably leads to light scattering and ultimately to opacity.
  • the decrease in the intensity of radiation of a defined wavelength when passing through a mixture shows a strong dependence on the diameter of the inorganic particles.
  • suitable substances would have to absorb in the UV range, appear as transparent and colorless as possible in the visible range, and be readily incorporated into polymers.
  • numerous metal oxides absorb UV light, for the reasons mentioned above, they are poorly soluble without adversely affecting the mechanical properties or the optical properties in the visible light range into polymers.
  • nanomaterials for dispersion in polymers requires not only the control of particle size but also the surface properties of the particles.
  • Simply mixing (e.g., by extrusion) hydrophilic particles with a hydrophobic polymer matrix results in uneven distribution of the particles throughout the polymer and also in their aggregation.
  • their surface must therefore be at least hydrophobically changed.
  • the nanoparticulate materials show a great tendency to form agglomerates, which remain even with a subsequent surface treatment.
  • these particles are ZnO particles having a particle size of 30 to 50 nm with a coating of a copolymer consisting essentially of lauryl methacrylate
  • LMA hydroxyethyl methacrylate
  • HEMA hydroxyethyl methacrylate
  • German patent applications DE 102005056621 and DE 102005056622 describe production processes for nanoparticles in which one or more precursors for the nanoparticles in an organic solvent are converted to the nanoparticles in a step a), and in a step b) the growth of the nanoparticles by addition at least one modifier, which may be a copolymer of at least one monomer having hydrophobic radicals and at least one monomer having hydrophilic radicals or an alkoxysilane, is terminated when, in the UV / VIS spectrum of the reaction solution, the absorption edge has reached the desired value, and its use for UV protection in polymers.
  • at least one modifier which may be a copolymer of at least one monomer having hydrophobic radicals and at least one monomer having hydrophilic radicals or an alkoxysilane
  • a first subject of the present invention are therefore nanoparticles with an average particle size determined by means of particle correlation spectroscopy (PCS) in the range of 3 to 50 nm, dispersed in an organic solvent, characterized in that they are obtainable by a process in which one or more precursors for the nanoparticles in an organic solvent with a compound M 3-x [ ⁇ 3-x SiRi + ⁇ ] are converted to the nanoparticles, where x is an integer selected from 0, 1 or 2, M is H, Li , Na or K and all R independently of one another represent a branched or unbranched, saturated or unsaturated hydrocarbon radical having 1 to 28 C atoms in which one or more C atoms may be replaced by O.
  • PCS particle correlation spectroscopy
  • the particles according to the invention are distinguished by high absorption in the UV range, particularly preferably in the UV-A range, combined with high transparency in the visible range. In contrast to many particle qualities known from the prior art, these properties of the particles according to the invention do not change during storage or only to a negligible extent.
  • the SiRi + x groups on the particle surface reduce the photocatalytic activity of the particles or their photocatalytic degradation.
  • the photocatalytic activity of the particles is significantly reduced (as shown in Example 4).
  • the production process according to the invention allows economical production of the particles, since higher solids contents can be achieved in the product suspension than using the customary hydroxide bases.
  • a better stabilization of the particles over a broader size range can be achieved so that the time window for the application of the modifying or compatibilizing layers is significantly greater.
  • Compatibilizing in the present application here means to functionalize the particles such that a conversion into organic, hydrophobic solvents, as is the case for many applications (eg in paints) is possible. This can be done, for example, by suitable hydrophobic silanes.
  • nanoparticles in preferred embodiments of the present invention are particles consisting essentially of oxides or hydroxides of silicon,
  • the particles according to the invention preferably have an average particle size determined by means of particle correlation spectroscopy (PCS) or by a transmission electron microscope of 5 to 20 nm, preferably 7 to 15 nm.
  • PCS particle correlation spectroscopy
  • the distribution of particle sizes is narrow, ie the d50 value, and in particularly preferred embodiments even the d90 value is preferably in the ranges indicated above from 5 to 15 nm, or even 7 to 12 nm.
  • the particles have a further surface modification, which is preferably a silica coating and / or a hydrophobic modification.
  • silica means a material consisting essentially of silicon dioxide and / or silicon hydroxide, it also being possible for the Si atoms to carry organic radicals which were already present in the modifiers.
  • Surface modifiers for hydrophobic modification are, for example, selected from the group of organofunctional silanes, quaternary ammonium compounds, phosphonates, phosphonium and sulfonium compounds or mixtures thereof.
  • a preferred surface modifier is an organofunctional silane, as described in more detail below.
  • the particles according to the invention contain a silica coating and additionally further with a surface modifier selected from the group of organofunctional silanes, quaternary ammonium compounds, phosphonates, phosphonium and sulfonium compounds or mixtures thereof.
  • a preferred surface modifier is an organofunctional silane, as further described in detail below, modified.
  • a further subject of the present invention is a corresponding production process, ie a process for the production of nanoparticles having an average particle size in the range from 3 to 50 nm dispersed in an organic solvent, characterized in that one or more precursors for the nanoparticles are reacted in an organic solvent with a compound M 3 - ⁇ [O 3-x SiRi + x ] to the nanoparticles, where x is one Whole number selected from 0, 1 or 2, M is H, Li, Na or K and each R independently represents a branched or unbranched, saturated or unsaturated hydrocarbon radical having 1 to 28 carbon atoms in which one or more C Atoms can be replaced by O.
  • water-soluble metal compounds preferably silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and / or zirconium compounds
  • precursors for the inorganic nanoparticles preferably are zinc salts of carboxylic acids, for example zinc acetate or halides.
  • mixed oxides can be obtained in a simple manner by suitable mixing of the corresponding precursors.
  • suitable precursors presents no difficulty to the person skilled in the art, all compounds which are suitable for precipitating the corresponding target compounds from aqueous solution are suitable.
  • An overview of suitable precursors for preparing oxides is given, for example, in Table 6 in K.
  • a base may be MOH, where M is Li, Na, or K, wherein the proportion of base in the total of M 3-x [ ⁇ 3 - ⁇ SiR 1 + x ] and base is up to 99.5 %. If an additional base MOH is to be used, the Proportion of base preferably 10-70 mol% based on the total amount or particularly preferably 30-60 mol%.
  • R is an alkoxy radical having 1 to 27 carbon atoms, preferably a methoxy or ethoxy radical.
  • x is 2 and all R are each independently methyl or ethyl.
  • M 3-x [ ⁇ 3-x SiRi + ⁇ ] all R are each independently methyl, ethyl, methoxy or ethoxy. It may further be preferred according to the invention if M is K. It is particularly preferred in a variant of the invention if x is 2 and the formula of the named compounds is correspondingly simplified to M [OSiR 3 ]. Very particularly preferred is the use of compounds of the formula K [OSiR 2 CH 3 ], with R, as indicated above, wherein all R are preferably methyl.
  • At least one modifier for producing a silica coating or a surface modifier is selected from the group organofunctional silanes, quaternary ammonium compounds, phosphonates, phosphonium and sulfonium compounds, is added to produce a hydrophobic shell.
  • the modifier which is a precursor for silica is preferably a trialkoxysilane or a tetraalkoxysilane, alkoxy preferably being methoxy or ethoxy, particularly preferably methoxy.
  • TMOS tetramethoxysilane
  • the addition of the modifier is usually carried out 1 to 50 minutes after the start of the reaction, preferably 10 to 40 minutes after the start of the reaction and more preferably after about 30 minutes.
  • At least one surface modifier is added after coating with a silica coating in a further reaction step, wherein the modifier is preferably organofunctional silanes, quaternary ammonium compounds, phosphonates, phosphonium and sulfonium compounds.
  • the nanoparticles almost agglomerate-free from the dispersions to isolate, since the individual particles form directly coated.
  • the nanoparticles obtainable by this method can be particularly easily and uniformly redispersed, in particular an undesired impairment of the transparency of such dispersions in the visible
  • Suitable surface modifiers are, for example, organofunctional silanes, quaternary silanes
  • the surface modifiers are selected from the group of organofunctional silanes.
  • the described requirements for a surface modifier fulfill an adhesion promoter which carries two or more functional groups.
  • One group of the coupling agent chemically reacts with the oxide surface of the nanoparticle.
  • Alkoxysilyl groups for example methoxy-, ethoxysilanes
  • halosilanes for example chlorine
  • acidic groups of phosphoric acid or phosphonic acids and phosphonic acid esters are suitable here.
  • the groups described are linked to a second, functional group.
  • the functional group is preferably acrylate, methacrylate, vinyl, amino, cyano, isocyanate, epoxy, carboxy or hydroxy groups.
  • Silane-based surface modifiers are described, for example, in DE 40 11 044 C2.
  • Phosphoric acid-based surface modifiers are available, inter alia, as Lubrizol® 2061 and 2063 from LUBRIZOL (Langer & Co.).
  • Suitable silanes are, for example, alkyltrimethoxysilanes with C3 to C18, vinyltrimethoxysilane, aminopropyltriethoxysilane, N-ethylamino-N-propyldimethoxysilane, isocyanatopropyltriethoxysilane, mercaptopropyltrimethoxysilane, vinyltriethoxysilane, Vinylethyldichlorosilane, vinylmethyldiacetoxysilane,
  • Methacryloxyethyltrimethoxysilane 2-acryloxyethyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-
  • 3-methacryloxypropyltrimethoxysilane and hexadecyltrimethoxysilane are commercially available e.g. at ABCR GmbH & Co.,
  • Vinylphosphonic acid or vinylphosphonic acid diethyl ester can also be listed here as adhesion promoters (manufacturer: Hoechst AG, Frankfurt am Main).
  • the surface modifier is an amphiphilic silane of 3 Si-Sp-P Ah -B h, where the radicals R are identical or Sp can be either -O- or straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2 -18 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms, Ah P represents a hydrophilic block, B hb is a hydrophobic block and wherein preferably at least one reactive functional group is present bound to Ah P and / or B hb is.
  • amphiphilic silanes contain a head group (R) 3 Si, where the radicals R may be the same or different and represent hydrolytically removable radicals. Preferably, the radicals R are the same.
  • Suitable hydrolytically removable radicals are, for example, alkoxy groups having 1 to 10 C atoms, preferably having 1 to 6 C atoms, halogens, hydrogen, acyloxy groups having 2 to 10 C atoms and in particular having 2 to 6 C atoms or NRV groups, the Radicals R 'may be the same or different and are selected from hydrogen or alkyl having 1 to 10 C atoms, in particular having 1 to 6 C atoms.
  • Suitable alkoxy groups are, for example, methoxy, ethoxy, propoxy or butoxy groups.
  • Suitable halogens are in particular Br and Cl.
  • Examples of acyloxy groups are acetoxy or propoxy groups. Oximes are also suitable as hydrolytically removable radicals.
  • the oximes may hereby be substituted by hydrogen or any organic radicals.
  • the radicals R are preferably alkoxy groups and in particular methoxy or ethoxy groups.
  • Covalently bonded to the above-mentioned head group is a spacer S P , which acts as a link between the Si head group and the hydrophilic block A hP and performs a bridging function in the context of the present invention.
  • the group Sp is either -O- or straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-18 C atoms and one or more triple bonds, saturated, partially or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms.
  • the C 1 -C 18 -alkyl group of Sp is, for example, a methyl, ethyl, isopropyl, propyl, butyl, sec-butyl or tert-butyl, and also pentyl, 1, 2- or 3-methylbutyl, 1, 1-, 1, 2- or 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl , Tridecyl or tetradecyl group.
  • it may be perfluorinated, for example as difluoromethyl, tetrafluoroethyl, hexafluoropropyl or octafluorobutyl.
  • a straight-chain or branched alkenyl having 2 to 18 C atoms, wherein several double bonds may also be present is, for example, vinyl, allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore 4-pentenyl, isopentenyl, Hexenyl, heptenyl, octenyl, -CgHi 6 , - C10H18 to -Ci 8 H 34 , preferably allyl, 2- or 3-butenyl, isobutenyl, sec-butenyl, furthermore preferred is 4-pentenyl, iso-pentenyl or hexenyl.
  • a straight-chain or branched alkynyl having 2 to 18 C atoms, wherein a plurality of triple bonds may also be present, is, for example, ethynyl, 1- or 2-propynyl, 2- or 3-butynyl, furthermore
  • Unsubstituted saturated or partially or fully unsaturated cycloalkyl groups having 3-7 C atoms may be cyclopropyl, cyclobutyl,
  • the spacer group Sp is followed by the hydrophilic block A hp .
  • This may be selected from nonionic, cationic, anionic or zwitterionic hydrophilic polymers, oligomers or groups.
  • the hydrophilic block is ammonium, sulfonium, phosphonium, alkyl chains with carboxyl, sulfate and phosphate side groups, which may also be present as a corresponding salt, partially esterified anhydrides with free acid or Salt group, OH-substituted alkyl or cycloalkyl chains (eg, sugars) having at least one OH group, NH- and SH-substituted alkyl or cycloalkyl chains or mono-, di- tri- or oligo-ethylene glycol groups.
  • the length of the corresponding alkyl chains can be 1 to 20 C atoms, preferably 1 to 6 C atoms.
  • nonionic, cationic, anionic or zwitterionic hydrophilic polymers, oligomers or groups can be prepared from corresponding monomers by polymerization in accordance with methods generally known to the person skilled in the art.
  • Suitable hydrophilic monomers contain at least one dispersing functional group which consists of the group consisting of (i) functional groups which can be converted by neutralizing agents into anions, and anionic groups, and / or (ii) functional groups which are neutralized by neutralizing agents and / or
  • Quaternizing agents can be converted into cations, and cationic groups, and / or
  • the functional groups (i) are selected from the group consisting of carboxylic acid, sulfonic acid and phosphonic acid groups, acidic sulfuric acid and
  • Phosphoric acid ester groups and carboxylate, sulfonate, phosphonate, sulfate ester and phosphate ester groups the functional groups (ii) from the group consisting of primary, secondary and tertiary amino groups, primary, secondary, tertiary and quaternary ammonium groups, quaternary phosphonium groups and tertiary sulfonium groups, and the functional groups (iii) are selected from the group consisting of omega-hydroxy and omega-alkoxy-poly (alkylene oxide) -1-yl groups.
  • the primary and secondary amino groups may also serve as isocyanate-reactive functional groups.
  • hydrophilic monomers having functional groups (i) are acrylic acid, methacrylic acid, beta-carboxyethyl acrylate, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; olefinically unsaturated sulfonic or phosphonic acids or their partial esters; or maleic acid mono (meth) acryloyloxyethyl ester, succinic acid mono (meth) acryloyloxyethyl ester or phthalic acid mono (meth) acryloyloxyethyl ester, in particular acrylic acid and methacrylic acid.
  • suitable hydrophilic monomers with functional groups (ii) are 2-aminoethyl acrylate and methacrylate or allylamine.
  • hydrophilic monomers having functional groups (iii) are omega-hydroxy or omega-methoxy-polyethylene oxide-1-yl, omega-methoxy-polypropylene oxide-1-yl or omega-methoxy-poly-ethylene oxide-co-polypropylene oxide.
  • Suitable monomers for the formation of zwitterionic hydrophilic polymers are those in which a betaine structure occurs in the side chain.
  • the side group is selected from - (CH 2 ) m - (N + (CH 3) 2) - (CH 2 ) n -SO 3 -, CH 2 ) m - (N + (CH 3 ) 2 ) - (CH 2 ) n -PO 3 2 -, - (CH 2 ) m - (N + (CH 3 ) 2) - (CH 2 ) n -O-PO 3 2 - orMeCH 2 ) m - (P + (CH 3) 2 MCH 2 ) n -SO 3 -, where m is an integer from the range of 1 to 30, preferably from the range 1 to 6, particularly preferably 2, and n is an integer from the range of 1 to 30, preferably from the range 1 to 8, particularly preferably 3.
  • At least one structural unit of the hydrophilic block has a phosphonium or sulfonium radical.
  • hydrophilic monomers it is to be noted that it is preferable to combine the hydrophilic monomers having functional groups (i) and the hydrophilic monomers having functional groups (ii) so as not to form insoluble salts or complexes. In contrast, the hydrophilic monomers with functional groups (i) or with functional groups (ii) be combined with the hydrophilic monomers having functional groups (iii) as desired.
  • the monomers having the functional groups (i) are particularly preferably used.
  • the neutralizing agents for the anionic functional groups (i) are selected from the group consisting of ammonia, trimethylamine, triethylamine, tributylamine, dimethylaniline, diethylaniline, triphenylamine, dimethylethanolamine, diethylethanolamine, methyldiethanolamine, 2-aminomethylpropanol, dimethylisopropylamine, dimethylisopropanolamine, triethanolamine , Diethylenetriamine and triethylenetetramine, and the neutralizing agents for the cation-convertible functional groups (ii) selected from the group consisting of sulfuric acid, hydrochloric acid, phosphoric acid, formic acid, acetic acid, lactic acid, dimethylolpropionic acid and citric acid.
  • the hydrophilic block is selected from mono-di- and triethylene glycol structural units.
  • the hydrophobic block B hb is based on hydrophobic groups or, like the hydrophilic block, on the polymerization of suitable hydrophobic monomers.
  • hydrophobic groups are straight-chain or branched alkyl having 1-18 C atoms, straight-chain or branched alkenyl having 2-18 C atoms and one or more double bonds, straight-chain or branched alkynyl having 2-18 C atoms and one or more triple bonds , saturated, partial or fully unsaturated cycloalkyl having 3-7 C atoms, which may be substituted by alkyl groups having 1-6 C atoms. Examples of such groups are already mentioned in advance.
  • aryl, polyaryl, aryl-C 1 -C 6 -alkyl or esters having more than 2 C atoms are suitable.
  • the groups mentioned may also be substituted, in particular with halogens, with perfluorinated groups being particularly suitable.
  • Aryl-C r C 6 -alkyl is, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, phenylpentyl or phenylhexyl, it being possible for both the phenyl ring and the alkylene chain to be partially or completely substituted by F as described above, more preferably benzyl or phenylpropyl.
  • hydrophobic olefinically unsaturated monomers examples include
  • substantially acid group-free esters of olefinically unsaturated acids such as (meth) acrylic acid, crotonic acid, ethacrylic acid, vinylphosphonic acid or vinylsulfonic acid alkyl or cycloalkyl esters having up to 20 carbon atoms in the alkyl radical, especially methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate, methacrylate, crotonate, ethacrylate or vinyl vinonate or vinyl sulfonate; cycloaliphatic (meth) acrylic acid, crotonic acid, ethacrylic acid, vinylphosphonic acid or
  • Vinylsulfonic acid esters in particular cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano-1H-indenemethanol or tert-butylcyclohexyl (meth) acrylate, crotonate, ethacrylate, vinyiphosphonate or vinylsulfonate.
  • higher-functional (meth) acrylic acid, crotonic acid or ethacrylic acid alkyl or cycloalkyl esters such as ethylene glycol, Propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1, 5-diol, hexane-1, 6-diol, octahydro-4,7-methano-1H-indenedimethanol or cyclohexane-1, 2-, -1, 3- or -1, 4-diol di (meth) acrylate, trimethylolpropane tri (meth) acrylate or pentaerythritol tetra (meth) acrylate and the analogous ethacrylates or crotonates.
  • minor amounts of higher-functional monomers (1) are amounts which do not lead to crosslinking or gelation of the polymers;
  • Carboxylic acids such as hydroxyalkyl esters of acrylic acid, methacrylic acid and ethacrylic acid, in which the hydroxyalkyl group up to 20
  • Containing carbon atoms such as 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3-hydroxybutyl, 4-hydroxybutyl acrylate, methacrylate or ethacrylate; 1, 4-bis (hydroxymethyl) cyclohexane, octahydro-4,7-methano-1H-indenedimethanol or methylpropanediol monoacrylate, monomethacrylate, monoethacrylate or monocrotonate; or reaction products of cyclic esters, e.g. epsilon-caprolactone and these hydroxyalkyl esters;
  • Allyl ethers of polyols such as trimethylolpropane monoallyl ether or pentaerythritol mono-, di- or triallyl ether.
  • the higher functionality monomers are generally used only in minor amounts.
  • minor amounts of higher-functional monomers are those To understand amounts which do not lead to crosslinking or gelation of the polymers,
  • the reaction of the acrylic or methacrylic acid with the glycidyl ester of a carboxylic acid having a tertiary alpha carbon atom may be carried out before, during or after the polymerization reaction.
  • the monomer (2) used is preferably the reaction product of acrylic and / or methacrylic acid with the glycidyl ester of Versatic® acid. This glycidyl ester is commercially available under the name Cardura® E10.
  • Formaldehyde adducts of aminoalkyl esters of alpha, beta-olefinically unsaturated carboxylic acids and of alpha, beta-unsaturated carboxylic acid amides such as N-methylol- and N, N-dimethylolaminoethyl acrylate, -aminoethyl methacrylate, -acrylamide and -methacrylamide; such as
  • Acryloxysilane and hydroxyl-containing olefinically unsaturated monomers prepared by reacting hydroxy-functional silanes with epichlorohydrin 30 and subsequent reaction of the intermediate with an alpha, beta-olefinically unsaturated carboxylic acid, in particular acrylic acid and
  • Methacrylic acid or its hydroxyalkyl esters
  • vinyl esters of alpha-branched monocarboxylic acids having 5 to 18 carbon atoms in the molecule such as the vinyl esters of Versatic® acid sold under the trademark VeoVa®;
  • cyclic and / or acyclic olefins such as ethylene, propylene, but-1-ene, pent-1-ene, hex-1-ene, cyclohexene, cyclopentene, norbornene, butadiene, isoprene, cyclopentadiene and / or dicyclopentadiene;
  • amides of alpha, beta-olefinically unsaturated carboxylic acids such as (meth) acrylamide, N-methyl-, N, N-dimethyl-, N-ethyl-,
  • vinyl aromatic hydrocarbons such as styrene, vinyltoluene or alpha-alkylstyrenes, especially alpha-methylstyrene;
  • nitriles such as acrylonitrile or methacrylonitrile
  • vinyl compounds selected from the group consisting of vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride; Vinylamides, such as N-vinylpyrrolidone; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and vinyl cyclohexyl ether; and vinyl esters such as vinyl acetate, vinyl propionate, and vinyl butyrate;
  • vinyl halides such as vinyl chloride, vinyl fluoride, vinylidene dichloride, vinylidene difluoride
  • Vinylamides such as N-vinylpyrrolidone
  • Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and vinyl cyclohe
  • Allyl compounds selected from the group consisting of allyl ethers and esters, such as propyl allyl ether, butyl allyl ether, ethylene glycol diallyl ether, trimethylolpropane triallyl ether or allyl acetate or allyl propionate; As far as the higher-functional monomers are concerned, what has been said above applies mutatis mutandis;
  • Siloxane or polysiloxane monomers which may be substituted with saturated, unsaturated, straight-chain or branched alkyl groups or other hydrophobic groups already mentioned above.
  • polysiloxane macromonomers having a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 to 2.5 ethylenically unsaturated double bonds per molecule such as polysiloxane macromonomers having a number average molecular weight Mn of 1,000 to 40,000 and an average of 0.5 have up to 2.5 ethylenically unsaturated double bonds per molecule; in particular polysiloxane macromonomers which have a number-average molecular weight Mn of 2,000 to 20,000, more preferably 2,500 to 10,000 and in particular 3,000 to 7,000 and an average of 0.5 to 2.5, preferably 0.5 to 1, 5, ethylenically unsaturated double bonds per molecule, as in DE 38 07 571 A 1 on pages 5 to 7, DE 37 06 095 A 1
  • carbamate or allophanate group-containing monomers such as acryloyloxy or methacryloyloxyethyl, propyl or butyl carbamate or allophanate; Further examples of suitable monomers containing carbamate groups are described in patents US 3,479,328 A 1, US 3,674,838 A 1, US 4,126,747 A 1, US 4,279,833 A 1 or US 4,340,497 A 1.
  • polymerization of the abovementioned monomers can be carried out in any manner known to those skilled in the art, for example by polyaddition or cationic, anionic or radical polymerizations. Polyadditions are preferred in this context, because they can be combined with each other in a simple manner different types of monomers, such as epoxides with dicarboxylic acids or isocyanates with diols.
  • the amphiphilic silanes according to the present invention have an HLB value in the range of 2-19, preferably in the range of 4-15.
  • the HLB value is defined as ⁇ ⁇ r , mass polar components ..
  • amphiphilic silanes are further distinguished by the fact that at least one reactive functional group is bound to A hp and / or B h b.
  • the reactive functional group 5 is present at the hydrophobic block B hb and there particularly preferably bound to the end of the hydrophobic block.
  • the headgroup (R ⁇ Si and the reactive functional group are spaced as much as possible, which allows a particularly flexible design of the chain lengths of the blocks A hp and Q B hb , without the possible reactivity of the reactive groups, for example with the surrounding medium to significantly reduce.
  • the reactive functional group can be selected from silyl groups with hydrolytically removable radicals, OH, carboxy, NH, SH groups, halogens or double bonds containing reactive groups, such as acrylate or vinyl groups.
  • Suitable silyl groups with hydrolytically removable radicals have already been described in advance in the description of the head group (R) 3 Si.
  • the reactive group is an OH group.
  • the process according to the invention can be carried out as described above.
  • the reaction in the process according to the invention is carried out in an organic solvent or solvent mixture.
  • Preferred solvents are alcohols or ethers, with the use of methanol, ethanol, diethyl ether, tetrahydrofuran and / or dioxane or mixtures thereof being particularly preferred.
  • methanol has proved to be a particularly suitable solvent.
  • the reaction temperature can be selected in the range between room temperature and the boiling point of the chosen solvent.
  • the reaction rate can be determined by appropriate selection of
  • Solvent can be controlled so that the skilled person no
  • Particle size is desired, using UV spectroscopy is possible.
  • an emulsifier preferably a nonionic surfactant.
  • Preferred emulsifiers are optionally ethoxylated or propoxylated, longer-chain alkanols or alkylphenols having different Ethoxylation or propoxylation degrees (eg adducts with 0 to 50 moles of alkylene oxide).
  • dispersants can be used advantageously, preferably water-soluble high molecular weight organic compounds with polar groups, such as polyvinylpyrrolidone, copolymers of
  • Copolymeriste of an acrylic ester and acrylonitrile, polyvinyl alcohols having different residual acetate content, cellulose ethers, gelatin, block copolymers, modified starch, low molecular weight, carbon- and / or sulfonic acid-containing polymers or mixtures of these substances can be used.
  • Particularly preferred protective colloids are polyvinyl alcohols having a residual acetate content of less than 40, in particular 5 to 39 mol .-% and / or vinylpyrrolidone / vinyl propionate copolymers having a vinyl ester content of less than 35, in particular 5 to 30 wt .-%.
  • reaction conditions such as temperature, pressure, reaction time
  • reaction time can be specifically set the desired property combinations of the required nanoparticles.
  • the corresponding setting of these parameters does not cause any difficulties for the skilled person. For example, you can work for many purposes at atmospheric pressure and room temperature.
  • the nanoparticles according to the invention are used in particular for UV protection in polymers.
  • the particles protect either the polymers themselves against degradation by UV radiation, or the polymer preparation containing the nanoparticles is - again used as a UV protection for other materials - for example in the form of a protective film or applied as a lacquer layer.
  • Polymer formulations consisting essentially of at least one polymer or a paint formulation, which are characterized in that the polymer nanoparticles according to the invention contains, are therefore further objects of the present invention.
  • the absorption edge of a dispersion with, for example, 0.001% by weight of the nanoparticles in the range 300-500 nm, preferably in the range up to 300-400 nm and particularly preferably in Range is 320 to 380 nm.
  • the invention therefore also nanoparticles with an average particle size determined by means
  • PCS Particle Correlation Spectroscopy
  • Another object of the invention is therefore also a method for producing such isolated nanoparticles, wherein the organic solvent is removed in a last step until drying.
  • PC polycarbonate
  • PETP polyethylene terephthalate
  • PI polyamide
  • PS polystyrene
  • PMMA polymethyl methacrylate
  • the incorporation can be carried out by conventional methods for the preparation of polymer preparations.
  • the polymer material can be mixed with isolated nanoparticles according to the invention, preferably in an extruder or kneader.
  • a particular advantage of the particles according to the invention with silane coating consists in the fact that only a small energy input is required for the homogeneous distribution of the particles in the polymer in comparison with the prior art.
  • the polymers may also be dispersions of polymers, such as, for example, paints or lacquer preparations.
  • the incorporation can be done by conventional mixing processes.
  • the good redispersibility of the particles according to the invention makes it easier to prepare such dispersions. Accordingly, dispersions of the particles according to the invention in polymers or solvents as dispersing medium are a further subject of the present invention.
  • the paints may be, for example, alkyd resin, chlorinated rubber, epoxy resin, acrylate resin, oil, nitro, polyester or
  • the solvents used in dispersions of the invention are preferably ether alcohols, aliphatics, alcohols, aromatics, chlorinated hydrocarbons, esters, hydroaromatics, ketones,
  • the surface or the underlying material under the coating for example, protect against UV radiation.
  • the measurements are carried out with a Zetasizer Nano ZS from Malvern at room temperature.
  • the measurement is carried out at a laser wavelength of 532 nm.
  • the sample volume is in all cases 1 ml at a concentration of 0.5% by weight of particles in butyl acetate.
  • the solutions are filtered with a 0.45 ⁇ m filter.
  • a Tecnai 2OF from Fei Company with field emission cathode is used.
  • the recordings are made at 200 kV acceleration voltage.
  • the solution containing the nanoparticles is diluted to 1 wt .-% and dropped a drop of this solution on a kohlebefilmtes Cu mesh and then immediately "sucked dry” with a filter paper, (blotting off excess solution). The measurement of the sample takes place after drying at room temperature for one day.
  • the particle dispersion is mixed with the paint, so that the ZnO content after drying the paint layer is 5%.
  • the paint is cured in a thick layer in a teflon pan, so that at least 2mm thick, free-standing films are formed. These samples are ultramicrotomed without embedding; at room temperature with 35 ° Diamond knife, section thickness 60 nm. The sections are suspended in water and transferred to coal-coated Cu nets and measured.
  • the conversion to zinc oxide and the growth of the nanoparticles can be monitored by UV spectroscopy. After only one minute reaction time, the absorption maximum remains constant, ie. ZnO formation is completed in the first minute.
  • a stable, transparent suspension is obtained which, according to UV spectroscopy and X-ray diffraction, contains ZnO.
  • the particle diameter after particle correlation spectroscopic examination with a Zetasizer Nano ZS from Malvern (PCS) is 4 -12 nm with a d50 of 6-7 nm and a d90 of 5-10 nm. The size is thus in the range of less than 15 -20nm, as needed for transparent applications.
  • the particles thus produced are stable for several hours, so that they can be further functionalized.
  • Example 1a After stirring at 50 ° C. for 30 minutes, 8.0 mmol of hexadecyltrimethoxysilane are added to the dispersion of Example 1a. The mixture is stirred for 5 h at 50 0 C. The separation of the hydrophobic particles is carried out by shaking with pentane or petroleum ether.
  • a stable, transparent suspension is obtained which, according to UV spectroscopy and X-ray diffraction, contains ZnO. Furthermore, no reflections of potassium acetate are visible in the X-ray diagram.
  • a new measurement after 10 days gives the same values as part of the measurement accuracy. Agglomeration of the particles can thus be excluded.
  • Spectrometer tracked. When the desired absorption edge is reached, 0.08 mol of hexadecyltrimethoxysilane are added and 5 hours stirred at 50 0 C. Thereafter, 1500 ml of petroleum benzine are added to the reaction mixture.
  • a stable, transparent suspension is obtained which, according to UV spectroscopy and X-ray diffraction, contains ZnO. Furthermore, no reflections of potassium acetate are visible in the X-ray diagram. The diameter of the particles is after
  • Example 2a Modification by TMOS addition
  • TMOS tetramethyl orthosilicate
  • a stable, transparent suspension is obtained which, according to UV spectroscopy and X-ray diffraction, contains ZnO.
  • the diameter of the particles is 4 -12 nm with a d50 of 6 to 7 nm and a d90 of 5 to 10 nm.
  • Example 2b Modification by TMOS addition and subsequent silanization
  • Example 2a After 60 min, 10.0 mmol hexadecyltrimethoxysilane be given to that described in Example 2a suspension under stirring at 50 0 C. The mixture is stirred for 5 h at 50 0 C. The separation of hydrophobic particles are made by shaking with pentane or petroleum ether.
  • a stable, transparent suspension is obtained which, according to UV spectroscopy and X-ray diffraction, contains ZnO. Furthermore, no reflections of potassium acetate are visible in the X-ray diagram. The diameter of the particles is after
  • Comparative Example 3 ZnO preparation with KOH A solution of 0.4 mol Zn (OAc) 2 * 2H2 ⁇ in 250 mL of methanol is heated to 50 0 C. For this purpose, a likewise heated to 50 0 C solution of 0.680 mol KOH in 250 mL of methanol is added with stirring.
  • the conversion to zinc oxide and the growth of the nanoparticles can be monitored by UV spectroscopy. After only 10 minutes, a white precipitate of zinc oxide precipitates. The reaction is continued for 5 hours. The precipitate is washed with methanol.
  • a white suspension is obtained which contains ZnO according to X-ray diffraction. Furthermore, no X-ray reflections of potassium acetate are visible.
  • isopropanol is used on photoactive surfaces via the intermediate acetone in the presence of Water vapor and oxygen is oxidized under irradiation to CO 2 .
  • the speed of this reaction is considered as a measure of the photoactivity of the substance being examined.
  • the intensity of the UV-A radiation acting on this substance is set to 15 mW / cm 2 immediately before the examination.
  • the software of the computer connected to the FTIR evaluates the respective experimental spectrum as the sum of the reference spectra of species involved in the degradation process. From the proportions of their intensity on the experimental spectrum, the concentration of each individual component in the gas phase can be calculated. The difference in the concentrations before and after the irradiation is a measure of the photocatalytic degradation. Table: Difference value from the measured
  • Injection molding processed to 1, 5 mm thick plates. These are transparent and exhibit ⁇ 5% at 350 nm,> 90% transmission at 450 nm, measured on the UV-vis spectrometer.
  • the components A and B are mixed and applied by means of a doctor blade to a glass plate with a layer thickness of 200 .mu.m.
  • the paint is at 130C for
  • this layer shows a transmission of over 95% at 400nm and less than 5% at 350nm.

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Abstract

L'invention concerne des nanoparticules, notamment des nanoparticules à surface modifiée, ayant une taille de particule moyenne, mesurée par spectroscopie par corrélation de photons (PCS) ou par microscopie à transmission d'électrons, comprise entre 3 et 50 nm, dispersée dans un solvant organique, caractérisées en ce qu'elles peuvent être obtenues par un procédé selon lequel un ou plusieurs précurseurs des nanoparticules sont mis en réaction dans un solvant organique avec un composé M3-x[O3(- )XSiR1-X] pour former les nanoparticules, x représentant un nombre entier choisi entre 0, 1 ou 2, M représentant H, Li, Na ou K et tous les R représentant, indépendamment les uns des autres, un radical hydrocarboné saturé ou insaturé, linéaire ou réticulé, ayant de 1 à 28 atomes de carbone, dans lequel un ou plusieurs atomes de carbone peuvent être remplacés par un oxygène, ainsi que son utilisation en tant que protection contre les UV dans des polymères.
EP07724958A 2006-05-24 2007-05-08 Nanoparticules Withdrawn EP2019848A1 (fr)

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EP2376564A2 (fr) 2008-12-12 2011-10-19 Basf Se Dispersions contenant des nanoparticules fonctionnalisées de type oxyde
CN102459471B (zh) 2009-06-24 2014-08-13 巴斯夫欧洲公司 改性ZnO纳米颗粒
WO2011023266A1 (fr) 2009-08-28 2011-03-03 Basf Se Nanoparticules modifiées
JP5748573B2 (ja) * 2011-06-15 2015-07-15 キヤノン株式会社 熱可塑性複合材料、その製造方法および成形品
EP2546319A1 (fr) * 2011-07-13 2013-01-16 Koninklijke Philips Electronics N.V. Composants de conversion lumineuse plastique haute efficacité par l'incorporation de phosphore dans un polymère par l'ajout de monomères avant la polymérisation
US8690964B2 (en) * 2011-10-11 2014-04-08 The Sweet Living Group, LLC Fabric having ultraviolet radiation protection
US9234310B2 (en) * 2011-10-11 2016-01-12 The Sweet Living Group, LLC Fabric having ultraviolet radiation protection, enhanced resistance to degradation, and enhanced resistance to fire
CN103050640B (zh) * 2013-01-29 2015-08-19 哈尔滨工业大学 一种氧化锌纳米颗粒/二氧化硅复合结构纳米棒的制备方法
JP2015066865A (ja) * 2013-09-30 2015-04-13 マツダ株式会社 積層塗膜及び塗装物
JP6477646B2 (ja) * 2016-09-29 2019-03-06 住友大阪セメント株式会社 分散液およびその製造方法、塗料、塗膜
JP7395919B2 (ja) * 2019-03-18 2023-12-12 東ソー株式会社 ポリマー被覆シリコン粒子
CN112779073B (zh) * 2021-01-05 2022-01-11 中国科学院兰州化学物理研究所 一种含有纳米氧化锌的预制稠化剂及其所得润滑脂组合物

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KR20060127929A (ko) * 2004-01-27 2006-12-13 메르크 파텐트 게엠베하 나노입자
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US20100092761A1 (en) 2010-04-15

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