EP1954632A1 - Nanoparticules - Google Patents

Nanoparticules

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Publication number
EP1954632A1
EP1954632A1 EP06818298A EP06818298A EP1954632A1 EP 1954632 A1 EP1954632 A1 EP 1954632A1 EP 06818298 A EP06818298 A EP 06818298A EP 06818298 A EP06818298 A EP 06818298A EP 1954632 A1 EP1954632 A1 EP 1954632A1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
polymer
copolymer
radicals
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06818298A
Other languages
German (de)
English (en)
Inventor
Matthias Koch
Gerhard Jonschker
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
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
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP1954632A1 publication Critical patent/EP1954632A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • 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
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • 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
    • Y10T428/254—Polymeric or resinous material
    • 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 modified zinc oxide nanoparticles, a production process for such particles and 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 therefore have to absorb in the UV range, appear as transparent as possible in the visible range and be readily incorporated into polymers. Although numerous metal oxides absorb UV light, they are poorly soluble for the reasons given above without impairing the mechanical or optical properties Incorporate visible light properties 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.
  • a method can be obtained in which in a step a) an inverse
  • Emulsion containing one or more water-soluble precursors for the nanoparticles or a melt is prepared by means of a random copolymer of at least one monomer having hydrophobic radicals and at least one monomer having hydrophilic radicals and in a step b) particles are produced.
  • 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) and hydroxyethyl methacrylate
  • HEMA The ZnO particles are produced, for example, by basic precipitation from an aqueous zinc acetate solution.
  • International patent application WO 2000/050503 describes a process for the preparation of zinc oxide gels by basic hydrolysis of at least one zinc compound in alcohol or an alcohol-water mixture, which comprises ripening the precipitate initially formed during the hydrolysis until the zinc oxide is completely flocculated, this precipitate is then compressed into a gel and separated from the supernatant phase.
  • a first subject of the present invention is therefore zinc oxide nanoparticles having an average particle size determined by particle correlation spectroscopy (PCS) in the range of 3 to 20 nm, whose particle surface is modified with at least one copolymer of at least one monomer having hydrophobic radicals and at least one monomer having hydrophilic radicals is dispersed in an organic solvent, characterized in that it can be obtained by a process in which in a step a) one or more precursors for the nanoparticles in an alcohol are converted to the nanoparticles, in a step b) the growth of the nanoparticles by adding at least one copolymer of at least one monomer having hydrophobic radicals and terminating at least one monomer having hydrophilic radicals when, in the UV / VIS spectrum of the reaction solution, the absorption edge has reached the desired value and optionally in step c) the alcohol from step a) is removed and replaced by another organic solvent.
  • PCS particle correlation spectroscopy
  • the ZnO nanoparticles according to the invention which are dispensed by the process described can also be isolated. This is achieved by removing the alcohol from step a) until it dries.
  • Another object of the present invention is a corresponding method for the production of zinc oxide nanoparticles having an average particle size determined by particle correlation spectroscopy (PCS) in the range of 3 to 20 nm, the particle surface with at least one copolymer of at least one monomer having hydrophobic radicals and at least one Monomer modified with hydrophilic radicals dispersed in an organic solvent, characterized in that in a step a) one or more precursors for the nanoparticles in an alcohol are converted to the nanoparticles, in a step b) the growth of the nanoparticles by adding at least a copolymer of at least one monomer with hydrophobic radicals and at least one monomer with hydrophilic radicals is terminated when, in the UV / VIS spectrum of the reaction solution, the absorption edge has reached the desired value and optionally in step c) the Alcohol removed from step a) and replaced by another organic solvent.
  • PCS particle correlation spectroscopy
  • the salt formed during ZnO formation is filtered off in step c).
  • the alcohol is distilled off from step a) to dryness, the residue is taken up in another organic solvent in which the salt load does not dissolve, the salt load is filtered and the organic solvent is distilled off again to dry.
  • 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 zinc oxide 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 particle size is determined in particular by means of particle correlation spectroscopy (PCS), the examination being carried out with a Malvern Zetasizer according to the operating instructions.
  • PCS particle correlation spectroscopy
  • the diameter of the particles, as the d50 or d90 value, is determined.
  • the use of the copolymers makes it possible to isolate the nanoparticles from the dispersions virtually free of agglomerates, since the individual particles are coated with the polymer immediately after their formation.
  • the nanoparticles obtainable by this method can be particularly easily and uniformly redispersed, in particular an undesired impairment of the transparency Such dispersions in visible light can be largely avoided.
  • the process according to the invention allows a simple separation of the by-products, so that expensive purification of the products can be dispensed with.
  • Copolymers which are preferably used according to the invention exhibit a weight ratio of structural units having hydrophobic radicals to structural units having hydrophilic radicals in the random copolymers which range from 1: 2 to 500: 1, preferably from 1: 1 to 100: 1 and more preferably from 7: 3 to 10: 1.
  • X and Y correspond to the radicals of conventional nonionic or ionic monomers and R 1 represents hydrogen or a hydrophobic side group, preferably selected from the branched or unbranched alkyl radicals having at least 4 carbon atoms in which one or several, preferably all hydrogen atoms may be replaced by fluorine atoms, and
  • R 2 is a hydrophilic side group which preferably has one or more phosphonate, phosphate, phosphonium, sulfonate, sulfonium, (quaternary) amine, polyol or polyether radicals, more preferably one or more hydroxyl radicals means that the respective groups are randomly distributed in the polymer, and within a molecule -XR 1 and -YR 2 may each have several different meanings and the copolymers in addition to the structural units shown in formula I further structural units, preferably those without or with short such as Ci -4 may contain alkyl side chains that meet requirements of the invention in a special way.
  • Particularly preferred according to the invention may be the use of random copolymers.
  • Such polymers and their preparation are described in International Patent Application WO 2005/070979, the disclosure of which relates expressly to the content of the present application.
  • R 2 preferably represents a side group - (CH 2 ) m - (N + (CH 3 ) 2 ) - (CH 2 ) n - SO 3 " or a side group - (CH 2) m - (N + (CH 3 ) 2) - (CH 2 ) n -PO 3 2 ' , - (CH 2 ) m -
  • At least one structural unit of the copolymer has a phosphonium or sulfonium radical.
  • Random copolymers can be prepared according to the following scheme:
  • LMA lauryl methacrylate
  • DMAEMA dimethylaminoethyl methacrylate
  • a copolymer consisting essentially of lauryl methacrylate (LMA) and hydroxyethyl methacrylate (HEMA) is used, which can be prepared in known manner by free radical polymerization with AIBN in toluene.
  • LMA lauryl methacrylate
  • HEMA hydroxyethyl methacrylate
  • Alternative preferred copolymers to be used may include styrene, vinylpyrrolidone, vinylpyridine, halogenated styrene or methoxystyrene, these examples being not limiting.
  • polymers are used, which are characterized in that at least one structural unit is an oligo- or polymer, preferably a macromonomer, with polyethers, polyolefins and polyacrylates being particularly preferred as macromonomers.
  • copolymers in addition to the at least one structural unit having hydrophobic radicals and at least one structural unit having hydrophilic radicals further structural units, those preferably without hydrophilic or hydrophobic side chains or with short side chains, such as 4 alkyl contain Ci.
  • the addition of the modifier takes place in the process according to the invention, as described above, depending on the desired absorption edge, but usually 1 to 20 hours after the start of the reaction, preferably 4 to 15 hours after the start of reaction and more preferably after 5 to 10 hours.
  • the location of the absorption edge in the UV spectrum is dependent on the particle size in the initial phase of zinc oxide particle growth. It is at the beginning of the reaction at about 300 nm and shifts in the course of time in the direction of 370 nm. By adding the modifier, the growth can be interrupted at any point. It is desirable to shift as close as possible to the visible region (from 400 nm) in order to achieve UV absorption over as wide a range as possible. If the particles are allowed to grow too far, the solution becomes cloudy.
  • the desired absorption edge is therefore in the range of 300-400 nm, preferably in the range up to 320-380 nm. Values between 355 and 365 nm have proven to be optimal.
  • Zinc salts can generally be used as precursors for the nanoparticles. Preference is given to using zinc salts of the carboxylic acids or halides, in particular zinc formate, zinc acetate or zinc propionate and also zinc chloride. Very particular preference is given to using zinc acetate or its hydrate according to the invention as precursor.
  • the reaction of the precursors with the zinc oxide takes place according to the invention preferably in the basic, wherein in a preferred process variant, a hydroxide base, such as LiOH, NaOH or KOH is used.
  • a hydroxide base such as LiOH, NaOH or KOH is used.
  • step a) is carried out in an alcohol in the process according to the invention. It has proven to be advantageous if the alkokhol is selected so that the copolymer used according to the invention is soluble in the alcohol itself. In particular, methanol or ethanol is suitable. Ethanol has proven to be a particularly suitable solvent for step a).
  • Suitable organic solvents or solvent mixtures for the dispersion of the nanoparticles according to the invention in addition to the alcohols in which they are initially obtained according to the method are typical paint solvents.
  • Typical lacquer solvents are, for example, alcohols, such as methanol or ethanol, ethers, such as diethyl ether, tetrahydrofuran and / or dioxane, esters, such as butyl acetate or hydrocarbons, such as toluene, petroleum ether, halogenated hydrocarbons, such as dichloromethane, or else commercially available products, such as solvent naphtha or products Shellsol, a high boiling point hydrocarbon solvent such as Shellsol A, Shellsol T, Shellsol D40 or Shellsol D70.
  • the particles according to the invention preferably have an average particle size determined by means of particle correlation spectroscopy (PCS) or transmission electron microscopy of 5 to 15 nm, in particular of 7 to 12 nm and very particularly preferably of about 10 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 preferably ranges from 5 to 15 nm, or even from 7 to 12 in the abovementioned ranges nm.
  • the measurement is carried out in a UV Vis spectrometer (Varian Carry 50).
  • the concentration of the solution is adapted to the device sensitivity (dilution to about 0.001 wt .-%).
  • reaction temperature can be selected in the range between room temperature and the boiling point of the selected solvent.
  • rate of reaction can be controlled by appropriate selection of the reaction temperature, the starting materials and their concentration and the solvent, so that it does not cause any difficulties for the skilled person, the speed be controlled so that a control of the reaction process by UV spectroscopy is possible.
  • emulsifiers are optionally ethoxylated or propoxylated, longer-chain alkanols or alkylphenols having different degrees of ethoxylation or propoxylation (for example adducts having from 0 to 50 mol of alkylene oxide).
  • Dispersing aids can also be used to advantage, preferably water-soluble high molecular weight organic compounds having polar groups, such as polyvinylpyrrolidone, copolymers of vinyl propionate or acetate and vinylpyrrolidone, partially saponified copolymer of 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.
  • polar groups such as polyvinylpyrrolidone, copolymers of vinyl propionate or acetate and vinylpyrrolidone, partially saponified copolymer of 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
  • 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 ⁇ / inylpropionat 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 in the temperature range between 30 and 50 ° C.
  • the nanoparticles according to the invention dispersed in an organic solvent or isolated, 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.
  • Polymers in which the isolated nanoparticles according to the invention can be well incorporated are in particular polycarbonate (PC), polyethylene terephthalate (PETP), polyimide (PI), polystyrene (PS), polymethyl methacrylate (PMMA) or copolymers which contain at least a portion of one of the polymers mentioned ,
  • 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 consists in the fact that, for the homogeneous distribution of the particles in the polymer, only a low energy input compared to the prior art is required.
  • the polymers may also be dispersions of polymers, such as, for example, paints.
  • the Incorporation by conventional mixing operations done.
  • 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 comprising at least 5 a polymer are a further subject of the present invention.
  • polymer preparations according to the invention comprising the isolated nanoparticles or the dispersions according to the invention are also particularly suitable for coating surfaces 10, for example of wood, plastics, fibers or glass.
  • the surface or the underlying material under the coating for example, protect against UV radiation.
  • LMA lauryl methacrylate
  • HEMA hydroxyethyl methacrylate
  • AIBN azoisobutyronitrile
  • 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. The absorption edge shifts with increasing reaction time to longer wavelengths. This can be correlated with sustained growth of ZnO particles by Ostwald ripening.
  • a comparative experiment without addition of the polymer solution shows continued particle growth and becomes cloudy on continued observation.
  • the ethanol is removed in vacuo and the remaining cloudy residue is dissolved with 10 ml of toluene.
  • the resulting in the reaction potassium acetate can be separated as a precipitate.
  • the supernatant clear solution also shows in the UV spectrum the characteristic absorption of zinc oxide.
  • UV spectroscopy and X-ray diffraction detect the formation of ZnO. Furthermore, no reflections of sodium acetate are visible in the X-ray diagram.
  • a dispersion of the particles from Example 2 in PMMA paint is prepared by mixing, applied to glass substrates and dried.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

L'invention concerne des nanoparticules d'oxyde de zinc présentant une granulométrie moyenne de 3 à 20 nm déterminée par spectroscopie de corrélation de particules, dont la surface est modifiée par l'intermédiaire d'au moins un copolymère composé d'au moins un monomère comportant des radicaux hydrophobes et d'au moins un monomère comportant des radicaux hydrophiles, lesdites particules étant dispersées dans un solvant organique. Les particules selon l'invention sont caractérisées en ce qu'elles peuvent être obtenues par l'intermédiaire d'un procédé consistant a) à transformer un ou plusieurs précurseurs de nanoparticules en nanoparticules dans un alcool ; b) à mettre un terme à la croissance des nanoparticules par addition d'au moins un copolymère composé d'au moins un monomère comportant des radicaux hydrophobes et d'au moins un monomère comportant des radicaux hydrophiles, lorsque le front d'absorption a atteint la valeur souhaitée dans le spectre UV/VIS de la solution de réaction ; et éventuellement c) à extraire l'alcool de l'étape a) et à remplacer celui-ci par un autre solvant organique. L'invention concerne également des nanoparticules isolées et leur utilisation pour la protection anti-UV dans des polymères.
EP06818298A 2005-11-25 2006-10-26 Nanoparticules Withdrawn EP1954632A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005056621A DE102005056621A1 (de) 2005-11-25 2005-11-25 Nanopartikel
PCT/EP2006/010330 WO2007059843A1 (fr) 2005-11-25 2006-10-26 Nanoparticules

Publications (1)

Publication Number Publication Date
EP1954632A1 true EP1954632A1 (fr) 2008-08-13

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP06818298A Withdrawn EP1954632A1 (fr) 2005-11-25 2006-10-26 Nanoparticules

Country Status (6)

Country Link
US (1) US20100221525A1 (fr)
EP (1) EP1954632A1 (fr)
KR (1) KR20080070865A (fr)
CN (1) CN101312911A (fr)
DE (1) DE102005056621A1 (fr)
WO (1) WO2007059843A1 (fr)

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FR2925059B1 (fr) * 2007-12-13 2012-08-17 Armines Procede de preparation d'un materiau polymere transparent comprenant un polycarbonate thermoplastique et des nanoparticules minerales modifiees en surface.
DE102008020441A1 (de) 2008-04-23 2009-10-29 Merck Patent Gmbh Klebstoff
DE102008024868A1 (de) 2008-05-23 2009-11-26 Merck Patent Gmbh Polymerisationsverfahren zur Herstellung von Kern-Hülle-Partikeln
KR101525523B1 (ko) 2008-12-22 2015-06-03 삼성전자 주식회사 반도체 나노 결정 복합체
TWI568811B (zh) * 2011-02-23 2017-02-01 歐米亞國際公司 包含含有次微米碳酸鈣粒子的塗佈組成物、其製備方法，以及含次微米碳酸鈣粒子於塗佈組成物中之用途
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CN101312911A (zh) 2008-11-26
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DE102005056621A1 (de) 2007-05-31

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