EP2288577A1 - Composition de dioxyde de titane contenant des nanoparticules de dioxyde de titane, sa préparation et son utilisation - Google Patents

Composition de dioxyde de titane contenant des nanoparticules de dioxyde de titane, sa préparation et son utilisation

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Publication number
EP2288577A1
EP2288577A1 EP09757507A EP09757507A EP2288577A1 EP 2288577 A1 EP2288577 A1 EP 2288577A1 EP 09757507 A EP09757507 A EP 09757507A EP 09757507 A EP09757507 A EP 09757507A EP 2288577 A1 EP2288577 A1 EP 2288577A1
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EP
European Patent Office
Prior art keywords
titanium dioxide
ethylenically unsaturated
meth
acrylate
composition
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Withdrawn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
EP09757507A
Other languages
German (de)
English (en)
Inventor
Virginie Bette
Roelof Balk
Alexandre Terrenoire
Harm Wiese
Ekkehard Jahns
Matthias Ballauff
Yan Lu
Martin Hoffmann
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP09757507A priority Critical patent/EP2288577A1/fr
Publication of EP2288577A1 publication Critical patent/EP2288577A1/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Withdrawn legal-status Critical Current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
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C09D5/028—Pigments; Filters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
    • 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
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/36—Compounds of titanium
    • C09C1/3607—Titanium dioxide
    • C09C1/3676—Treatment with macro-molecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • 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
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/22—Rheological behaviour as dispersion, e.g. viscosity, sedimentation stability
    • C—CHEMISTRY; METALLURGY
    • 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
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31692—Next to addition polymer from unsaturated monomers
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood
    • Y10T428/31899—Addition polymer of hydrocarbon[s] only
    • Y10T428/31902—Monoethylenically unsaturated

Definitions

  • EP 1 512 728 A1 describes photocatalytic coating compositions, composite materials and processes for their preparation.
  • the photocatalytic coating composition contains: (a) photocatalytically active oxide particles, (b) an emulsion of a hydrophobic resin, and (c) water. They are used to produce self-cleaning exterior coatings. Titanium dioxide particles are used as the photocatalyst, among others.
  • a first aspect of the invention is therefore a process for preparing a titanium dioxide composition containing titania nanoparticles by subjecting a hydrolyzable titanium compound to hydrolysis in the presence of polymer particles having a hydrophobic core and polyelectrolyte side chains attached thereto.
  • the titanium dioxide composite compositions are used in the form of a dispersion in an aqueous medium.
  • Liquid titanium dioxide composite compositions can be obtained in the form of a stable dispersion (special suspension).
  • the polymer particles with associated Ti ⁇ 2 nanoparticles form the disperse phase.
  • Associated TiO 2 nanoparticles are understood to be immobilized in the sphere of the polyelectrolyte side chains. Outside this sphere, the liquid titanium dioxide composite compositions according to the invention have essentially no free
  • These polymer particles can be obtained, for example, by first subjecting at least one hydrophobic ⁇ , ⁇ -ethylenically unsaturated monomer (M1) to free-radical polymerization to obtain the polymer particles forming the core and then, in a second stage, to subjecting the polyelectrolyte side chains to the polymer particles forming the core grafted.
  • M1 hydrophobic ⁇ , ⁇ -ethylenically unsaturated monomer
  • Suitable crosslinkers are z. As acrylic esters, methacrylic esters, allyl ethers or vinyl ethers of at least dihydric alcohols. The OH groups of the underlying alcohols may be completely or partially etherified or esterified; however, the crosslinkers contain at least two ethylenically unsaturated groups.
  • crosslinking agents are the acrylic acid amides, methacrylic acid amides and N-allylamines of at least divalent amines.
  • Such amines are for. B. 1, 2-diaminoethane, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 6-diaminohexane, 1, 12-dodecanediamine, piperazine, diethylenetriamine or isophoronediamine.
  • amides of allylamine and unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, or at least dibasic carboxylic acids, as described above.
  • the crosslinker (if present) is preferably in an amount of 0.0005 to 5 wt .-%, preferably 0.001 to 2.5 wt .-%, in particular 0.01 to 1, 5 wt .-%, based on the total weight the core forming monomers used for the polymerization used.
  • a seed latex can be used to polymerize the polymer particles forming the core.
  • the polymer particles forming the core can be subjected to functionalization on their surface before the grafting reaction in the second stage.
  • the polymer particles forming the core can be subjected to copolymerization with an ⁇ , ⁇ -ethylenically unsaturated photoinitiator in a specific embodiment.
  • Suitable copolymerizable photoinitiators are, for. As described in EP 0 217 205, which is incorporated herein by reference.
  • HMEM 2- [4- (2-hydroxy-2-methylpropionyl) phenoxy] -ethyl methacrylate
  • HMEM can be prepared by reacting methacrylic acid chloride with Irgacure ⁇ 2959 (4- (2-Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, available from Ciba Spezialitätenchemie, Switzerland) according to the method of Guo, X., Weiss, A. and Ballauf, M. in Macromolecules, 1999, 32, pp. 6043-6046.
  • the addition of the ⁇ , ß-ethylenically unsaturated photoinitiator is preferably under "starved conditions".
  • a slow addition rate is selected, which is preferably less than 0.5 mL / min, more preferably less than 0.1 mL / min.
  • the photoinitiator modified core particles are then subjected to photoemulsion polymerization in a second step to graft the polyelectrolyte side chains onto the core forming polymer particles.
  • the ionogenic and / or ionic groups are preferably anionogenic and / or anionic groups.
  • Suitable monomers (M2) having a free-radically polymerizable ⁇ , ⁇ -ethylenically unsaturated double bond and at least one anionogenic and / or anionic group per molecule are ethylenically unsaturated carboxylic acids and sulfonic acids or salts thereof.
  • the monomer (M2) is preferably selected from acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, the half ester of monoethylenically unsaturated dicarboxylic acids with 4 to 10, preferably 4 to 6 carbon atoms, for.
  • monomers (M3) selected from primary amides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids, N-vinylamides of saturated monocarboxylic acids, N-vinyllactams, N-alkyl and N, N-dialkylamides of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids, esters ⁇ , ⁇ ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-alkanediols, amides of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group, vinyl ethers, and mixtures thereof.
  • liquid titanium dioxide composite compositions in the form of a stable suspension.
  • liquid titanium dioxide composite compositions according to the invention have no precipitate even after months of storage.
  • the polymer particles with TiO 2 nanoparticles associated therewith are generally colloidally suspended.
  • the TiO 2 nanoparticles obtained by the process according to the invention are present exclusively in the anatase modification.
  • the modification can be determined by X-ray diffraction (XRD) of the titanium dioxide composite particles. All diffraction peaks can be assigned to the anatase modification of TiO2 (as found in the powder diffraction file number (PDF-No.): 00-021-1272 in the ICDD database). Clues for other crystal modifications are not found.
  • step a) With respect to the use in step a) suitable and preferred polymer particles having a hydrophobic core and polyelectrolyte side chains attached thereto, the previous implementation is fully incorporated by reference.
  • the organic solvent used is an alkanol whose alkyl radical corresponds to the alkyl radicals of the tetraalkyl orthotitanate or tetraalkyl orthosilicate used for the hydrolysis.
  • tetraethyl orthotitanate TEOT
  • ethanol ethanol
  • the particle sizes of the resulting titanium dioxide nonunits can be controlled via the molar ratio of water to hydrolyzable titanium compound. If z.
  • TEOT is used as a hydrolyzable titanium compound and the molar ratio of water to TEOT is about 2.3: 1, titanium dioxide nanoparticles are obtained which have an average particle size, determined by means of transmission electron microscopy, of about 4 nm.
  • TEOT is used as the hydrolyzable titanium compound and the molar ratio of water to TEOT is about 11.5: 1, titanium dioxide nanoparticles having an average particle size as determined by transmission electron microscopy of about 12 nm are obtained.
  • the ratio by weight of water-miscible organic solvent to water is preferably at least 10: 1, particularly preferably at least 100: 1, in particular at least 200: 1.
  • the temperature in step b) is at most 60 0 C, particularly preferably not more than 40 0 C.
  • the addition of the hydrolyzed sierbaren titanium compound to the dispersion in step b) at about ambient temperature. It is noteworthy that the TiO 2 particles produced by the process according to the invention at such low temperatures are crystalline without the need for heat treatment. Surprisingly, it has been found that it is advantageous if, over the addition time in step b), a maximum concentration of titanium compound to be hydrolyzed in the dispersant is not exceeded.
  • irregular, polydisperse titanium dioxide particles may form, which are not homogeneously embedded in the polyelectrolyte side chains of the spherical polyelectrolyte brush particles (SPB).
  • the metered addition of the hydrolyzable titanium compound over the metering time is therefore controlled to form substantially monodisperse spherical titanium dioxide nanoparticles homogeneously embedded in the SPB.
  • the hydrolyzable titanium compound is added at a substantially constant volume flow to the dispersion of polymer particles having a hydrophobic core and polyelectrolyte side chains attached thereto.
  • the titanium dioxide composite composition in liquid form obtained by the process according to the invention, especially by the steps a) and b), may additionally be subjected to a further work-up. These include z. As a cleaning and / or drying and / or a solvent exchange. Preference is therefore given to a process comprising the aforementioned steps a) and b), wherein additionally
  • step c) subjects the titanium dioxide composite composition obtained in step b) to a cleaning and / or drying and / or a solvent exchange.
  • the purification can be carried out by customary methods known to the person skilled in the art.
  • the liquid phase is separated with the impurities contained in the titanium dioxide composite particles for cleaning.
  • the separation can z. B. by sedimentation or membrane filtration.
  • the usual centrifuges or membranes with a suitable cut-off to retain the titania composite particles can be used.
  • the separated titanium dioxide composite particles may be subjected to a wash with a liquid wash medium.
  • Suitable washing media are those in which the titanium dioxide composite particles do not dissolve or release the associated titanium dioxide.
  • Preferred washing media are the water-miscible organic solvents described above and their mixtures with water. Particularly preferably, the washing medium is selected from water and water / alkanol mixtures.
  • a water / ethanol mixture is used as the washing medium.
  • the separation of the washing medium in turn carried out by sedimentation or membrane filtration.
  • the drying of the titanium dioxide composite composition can likewise be carried out by customary methods known to the person skilled in the art. If desired, prior to drying, the main amount of the dispersing z. B. be removed by sedimentation or membrane filtration. Suitable drying methods are z. As spray drying, fluidized spray drying, drum drying or freeze drying. Preferably, the drying takes place at a temperature of at most 100 0 C, more preferably of at most 80 0 C, in particular of at most 60 0 C instead.
  • the titanium dioxide composite compositions according to the present invention as polymer particles having a hydrophobic core and polyelectrolyte side chains bonded thereto, specifically comprise a polymer comprising a polystyrene core surface-crosslinked by copolymerization with methacrylic acid 2- [4- (2-hydroxy-2-methylpropionyl ) - Phenoxy] ethyl ester is modified and has grafted on side chains which contain copolymerized sodium styrene-4-sulfonate.
  • the solids content of the suspensions according to the invention is preferably 0.5 to 10 wt .-%, more preferably 1 to 5 wt .-%.
  • the titanium dioxide composite compositions according to the invention have a titanium dioxide content of at least 10% by weight, more preferably at least 15% by weight. %, especially at least 18 wt .-%, based on the total weight of solid titanium dioxide composite compositions or the total solids content in liquid titanium dioxide composite compositions.
  • the TiO 2 content of the TiO 2 nanocomposite can be determined by means of thermogravimetry (TGA).
  • the average particle diameter of the titanium dioxide nanoparticles contained in the titanium dioxide composite compositions according to the invention is preferably in the range from 3 to 50 nm, more preferably from 3.5 to 40 nm, in particular from 4 to 25 nm.
  • the particle size distribution is preferably in the Essentially unimodal.
  • the titanium dioxide nanoparticles contained in the titanium dioxide composite compositions of the present invention are crystalline. According to XRD, they are exclusively available in the anatase modification.
  • step b) subjecting the titanium dioxide composite composition obtained in step b) to drying, if appropriate after purification, and
  • step d) subjecting the dried titanium dioxide composite composition obtained in step c) to calcination.
  • step c With regard to the cleaning and drying, reference is made to the previous statements on step c).
  • the calcination may take place under inert (for example nitrogen or noble gases such as argon or helium), oxidizing (for example oxygen or air) or varying atmospheres (initially inert then oxidizing atmosphere). It is known to the person skilled in the art that mixtures of the gases mentioned can also be used. It may be thermally treated under a stagnant or flowing atmosphere, preferably a treatment is carried out under a flowing gas stream. A constant supply of fresh gas is preferred before a gas recycle.
  • the Composition of the atmosphere can be varied as a function of calcination temperature and time. Also possible is a moving thermal treatment, for example by rotary calcination drums, shaking or fluidization. The duration of calcination is usually in the range of 1 minute to 24 hours, preferably 5 minutes to 12 hours.
  • the calcination in step d) takes place in an inert atmosphere.
  • step d) takes place in an oxidizing atmosphere.
  • the calcination in step d) takes place in a first stage in an inert atmosphere and in a second stage in an oxidizing atmosphere.
  • the invention also relates to the titania compositions obtained after the calcination.
  • the titanium dioxide compositions obtained after calcination in an inert atmosphere preferably consist of at least 90% by weight, more preferably at least 95% by weight, in particular at least 99% by weight, of titanium dioxide and carbon.
  • the titanium dioxide compositions obtained after calcination in an oxidizing atmosphere and those after calcination in a first stage in an inert atmosphere and in a second stage in an oxidizing atmosphere are preferably at least 90% by weight, more preferably at least 95% by weight .-%, in particular at least 99 wt .-% of titanium dioxide.
  • the titania compositions obtained after calcination are characterized by their porous structure.
  • calcination can remove the polymer particles (SPB template) used as template in the hydrolysis, resulting in a porous structure.
  • the invention also relates to the titanium dioxide compositions in the form of a carbon-modified titanium dioxide composition having a porous structure which are obtainable by the process described above. Due to their large carbon-coated surface, they are of potential interest as catalysts, e.g. B. for hydrogenation reactions. They also serve as important intermediates for the preparation of titania compositions having a porous structure described below by subsequent calcination in an oxidizing atmosphere.
  • the invention also provides the titanium dioxide porous structure compositions obtainable by the method described above.
  • the template polymer particles When the calcination is carried out in a first stage in an inert atmosphere (eg under an argon atmosphere) and in a second stage in an oxidizing atmosphere (eg in the presence of air), the template polymer particles also become substantially complete away.
  • an inert atmosphere eg under an argon atmosphere
  • an oxidizing atmosphere eg in the presence of air
  • the comparison of the FE-SEM images for the different heat treatments of the Ti ⁇ 2 nanocomposite particles clearly shows that similarly porous surface morphologies are obtained.
  • the titanium dioxide compositions of this invention are characterized by a network of mesoporous and macroporous titania nanoparticles.
  • the titanium dioxide nanoparticles are crystalline and are present in the anatase modification.
  • porous materials are defined according to their pore size as follows: microporous: pore diameter ⁇ 2 nm, mesoporous: pore diameter between 2 and 50 nm and macroporous: pore diameter> 50 nm.
  • the macropores of the titanium dioxide compositions according to the invention preferably have an average pore diameter (determined by FESEM (field emission scanning electron microscope) analysis) in the range from greater than 50 to 200 nm, particularly preferably from 75 to 150 nm.
  • the size of the macropores can be controlled by the size of the core of the polymer particles used as a template.
  • the mesopores of the titanium dioxide compositions according to the invention preferably have an average pore diameter (determined by BET analysis) in the range from 2 to 30 nm, particularly preferably from 5 to 20 nm.
  • the size of the mesopores can be controlled by the length and grafting density of the polyelectrolyte side chains of the polymer particles used as a template.
  • the surface area of the titanium dioxide compositions according to the invention is preferably at least 50 m 2 / g, more preferably at least 60 m 2 / g.
  • the surface of the titanium dioxide compositions according to the invention can generally be increased significantly, preferably by at least 50%, more preferably by at least 75%.
  • the titanium dioxide compositions according to the invention are distinguished by a very good photocatalytic activity.
  • Ti ⁇ 2 can absorb photons under UV light irradiation and reacts directly with H2O, O2, and OH groups to produce reactive oxygen species.
  • the photocatalytic activity of the titanium dioxide compositions according to the invention, both in the form of the composites, as well as after calcining, can, for. B. by measuring the degradation of the organic dye rhodamine B (RhB) in the presence of the titanium dioxide compositions are occupied. This can z.
  • the reaction kinetics can be monitored by UVA / IS spectroscopy.
  • RhB After the addition of TiO 2 nanocomposite particles, the absorption band of RhB decreased rapidly at 552 nm under UV irradiation and exhibited a marked blue shift, indicating the formation of N-diethylated intermediates during the photocatalytic decomposition of RhB.
  • the titanium dioxide compositions according to the invention are suitable for use as or in a catalyst with photocatalytic activity and for the production of solar cells. They are especially suitable as a component for the production of coating compositions.
  • Titanium dioxide in the anatase modification is advantageously suitable for use in coating compositions, since these have a high soiling resistance as a result of their very hydrophilic as well as strongly oxidative surfaces.
  • Responsible Photocatalytic effects of anatase which form radicals under the influence of UV light, atmospheric oxygen and water, are among the reasons for this.
  • the surfaces of anatase-containing coating compositions often also have antimicrobial properties.
  • aqueous coating compositions based on the titanium dioxide compositions according to the invention lead to surface coatings with advantageous properties. These have especially hydrophilic and / or antimicrobial and / or soiling-resistant properties and / or show a reduced chalking and yellowing tendency.
  • Another object of the invention is therefore a binder composition consisting of or containing
  • At least one titania composition as defined above At least one titania composition as defined above.
  • the titanium dioxide composition may, if desired, be in solid form, e.g. B. in powder form, or in liquid form, for. B. in an aqueous medium, are used to prepare a binder composition of the invention.
  • Titanium dioxide composition in the form of a composite composition containing titanium dioxide nanoparticles associated with polymer particles having a hydrophobic core and attached polyelectrolyte side chains are preferably used as a suspension or in powder form.
  • Calcined titanium dioxide compositions are preferably used in powder form. The use of carbonaceous calcined titanium dioxide compositions is not preferred.
  • the preparation of the emulsion polymer can be carried out by free-radical aqueous emulsion polymerization by customary methods known to the person skilled in the art.
  • the titanium dioxide composition can also be added before and / or during the emulsion polymerization for the preparation of the emulsion polymer.
  • the addition of the titanium dioxide composition to the finished emulsion polymer is particularly preferred.
  • An addition after the emulsion polymerization also includes an addition in the context of the formulation of a product which contains an emulsion polymer based on at least one ⁇ , ß-ethylenically unsaturated monomer M).
  • a product which contains an emulsion polymer based on at least one ⁇ , ß-ethylenically unsaturated monomer M.
  • at least one titanium dioxide composition as defined above, as an additive z.
  • a paint or a paper coating As a paint or a paper coating.
  • At least one ⁇ , ß-ethylenically unsaturated monomer Mo is used, which is preferably selected from esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C2o-alkanols, vinyl aromatics, esters of vinyl alcohol with Ci C3o monocarboxylic acids, ethylenically unsaturated nitriles, vinyl halides, vinylidene halides, monoethylenically unsaturated carboxylic and sulfonic acids, phosphorus-containing monomers, esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o alkanediols, amides ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with C2-C3o-amino alcohols having a primary or secondary amino group, primary amides
  • Suitable esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C2o-alkanols are methyl (meth) acrylate, methyl methacrylate, ethyl (meth) acrylate, ethyl methacrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n Butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, tert-butyl methacrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl ( meth) acrylate,
  • Preferred vinyl aromatic compounds are styrene, 2-methylstyrene, 4-methylstyrene,
  • Suitable esters of vinyl alcohol with Ci-C3o-monocarboxylic acids are, for. Vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl laurate, vinyl stearate, vinyl propionate, vinyl versatate and mixtures thereof.
  • Suitable ethylenically unsaturated nitriles are acrylonitrile, methacrylonitrile and mixtures thereof.
  • Suitable vinyl halides and vinylidene halides are vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride and mixtures thereof.
  • Suitable ethylenically unsaturated carboxylic acids and sulfonic acids or derivatives thereof are acrylic acid, methacrylic acid, ethacrylic acid, ⁇ -chloroacrylic acid, crotonic acid, maleic acid, maleic anhydride, itaconic acid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid, fumaric acid, the half esters of monoethylenically unsaturated dicarboxylic acids having 4 to 10 , preferably 4 to 6 C atoms, for.
  • maleic acid monomethyl ester vinylsulfonic acid, allylsulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-acryloxypropylsulfonic acid, 2-hydroxy-3-methacryloxypropylsulfonic acid, styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid.
  • z 2-acrylamido-2-methylpropanesulfonic acid.
  • styrene sulfonic acids such as styrene-4-sulfonic acid and styrene-3-sulfonic acid and the alkaline earth or alkali metal salts thereof, for.
  • sodium styrene-3-sulfonate and sodium styrene-4-sulfonate are particularly preferred.
  • acrylic acid, methacrylic acid and mixtures thereof are particularly preferred.
  • Examples of phosphorus-containing monomers are, for.
  • vinylphosphonic acid and allyl phosphonic acid are also suitable.
  • diesters of phosphonic acid and phosphoric acid which are readily alkylated with a hydroxyalkyl (meth) and additionally simply with a different alcohol, eg. As an alkanol, are esterified.
  • Suitable hydroxyalkyl (meth) acrylates for these esters are those mentioned below as separate monomers, in particular 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate,
  • Corresponding dihydrogen phosphate ester monomers include phosphoalkyl (meth) acrylates such as 2-phosphoethyl (meth) acrylate, 2-phosphopropyl (meth) acrylate, 3-phosphopropyl (meth) acrylate, phosphobutyl (meth) acrylate and 3-phospho-2-hydroxypropyl (meth) acrylate. Also suitable are the esters of phosphonic acid and phosphoric acid with alkoxylated hydroxyalkyl (meth) acrylates, eg.
  • n is 1 to 50.
  • phosphoalkyl crotonates phosphoalkyl maleates, phosphoalkyl fumarates, phosphodialkyl (meth) acrylates, phosphodialkyl crotonates and allyl phosphates.
  • Further suitable phosphorus-containing monomers are described in WO 99/25780 and US 4,733,005, to which reference is hereby made.
  • Suitable esters of ⁇ , ß-ethylenically unsaturated mono- and dicarboxylic acids with C 2 -C 3o-alkanediols are, for. 2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 6-hydroxyhexyl acrylate, 6-hydroxyhexyl methacrylate, 3-hydroxy-2-ethylhexyl acrylate, 3-hydroxy-2-ethylhexyl methacrylate, etc.
  • Suitable primary amides of ⁇ , ß-ethylenically unsaturated monocarboxylic acids and their N-alkyl and N, N-dialkyl derivatives are acrylic acid amide, methacrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide , N- (n-butyl) (meth) acrylamide, N- (tert-butyl) (meth) acrylamide, N- (n-octyl) (meth) acrylamide, N- (1,1,3,3-tetramethylbutyl ) (meth) acrylamide, N-ethylhexyl (meth) acrylamide, N- (n-nonyl) (meth) acrylamide, N- (n-decyl) (meth) acrylamide,
  • N-vinyl lactams and derivatives thereof are, for. N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, N-vinyl-5-methyl-2-pyrrolidone, N-vinyl-5-ethyl-2-pyrrolidone, N-vinyl-6-methyl-2-piperidone, N-vinyl-6-ethyl-2-piperidone, N-vinyl-7-methyl-2-caprolactam, N-vinyl-7-ethyl-2-caprolactam, etc.
  • Suitable open-chain N-vinyl amide compounds are, for example, N-vinylformamide, N-vinyl-N-methylformamide, N-vinylacetamide, N-vinyl-N-methylacetamide, N-vinyl-N-ethylacetamide, N-vinylpropionamide, N-vinyl-N-methylpropionamide and N-vinylbutyramide.
  • Suitable esters of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with amino alcohols are N, N-dimethylaminomethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate and N, N-dimethylaminocyclohexyl (meth) acrylate.
  • Suitable amides of ⁇ , ⁇ -ethylenically unsaturated mono- and dicarboxylic acids with diamines which have at least one primary or secondary amino group are N- [2- (dimethylamino) ethyl] acrylamide, N- [2- (dimethylamino) ethyl] methacrylamide, N- [3- (dimethylamino) propyl] acrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N- [4- (dimethylamino) butyl] acrylamide, N- [4- (dimethylamino) butyl] methacrylamide, N- [2- (diethylamino) ethyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] acrylamide, N- [4- (dimethylamino) cyclohexyl] methacrylamide, etc.
  • Suitable monomers Mo are furthermore N, N-diallylamines and N, N-diallyl-N-alkylamines and their acid addition salts and quaternization products.
  • Alkyl is preferably Ci-C24-alkyl. Preference is given to N, N-diallyl-N-methylamine and N, N-diallyl-N, N-dimethylammonium compounds, such as. As the chlorides and bromides.
  • Suitable monomers Mo are also vinyl- and allyl-substituted nitrogen heterocycles, such as N-vinylimidazole, N-vinyl-2-methylimidazole, vinyl- and allyl-substituted heteroaromatic compounds, such as 2- and 4-vinylpyridine, 2- and 4-allylpyridine, and the salts thereof.
  • Suitable C 2 -C 8 -monoolefins and non-aromatic hydrocarbons having at least two conjugated double bonds are, for example, ethylene, propylene, isobutylene, isoprene, butadiene, etc.
  • Suitable polyether (meth) acrylates are compounds of the general formula (A)
  • H 2 C C - CY (CH 2 CH 2 O) k (CH 2 CH (CH 3 ) O), Ra
  • k and I independently of one another represent an integer from 0 to 100, the sum of k and I being at least 3,
  • R a is hydrogen, C 1 -C 6 -alkyl, C 5 -C 8 -cycloalkyl or Ce-Cu-aryl,
  • R b is hydrogen or C 1 -C 8 -alkyl
  • Y is O or NR C , wherein R c is hydrogen, C 1 -C 8 -alkyl or C 5 -C 8 -cycloalkyl.
  • k is an integer from 3 to 50, especially 4 to 25.
  • I is an integer from 3 to 50, in particular 4 to 25.
  • R a in the formula (A) is hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, n-pentyl, n-hexyl, octyl, 2-ethylhexyl, decyl, lauryl, PaI - mityl or stearyl.
  • R b is preferably hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl or n-hexyl, in particular hydrogen, methyl or ethyl.
  • R b is particularly preferably hydrogen or methyl.
  • Y in the formula (A) is O.
  • At least one polyether (meth) acrylate is used in the free-radical emulsion polymerization. This is then preferably used in an amount of up to 25% by weight, preferably up to 20% by weight, based on the total weight of the monomers Mo). It is particularly preferred to use 0.1 to 20% by weight, preferably 1 to 15% by weight, of at least one polyether (meth) acrylate for the emulsion polymerization. Suitable polyether (meth) acrylates are, for.
  • poly-condensation products of the aforementioned ⁇ , ß-ethylenically unsaturated mono- and / or dicarboxylic acids and their acid chlorides, amides and anhydrides with lyetherolen can be readily prepared by reacting ethylene oxide, 1,2-propylene oxide and / or epichlorohydrin with a starter molecule, such as water or a short-chain alcohol R a -OH.
  • a starter molecule such as water or a short-chain alcohol R a -OH.
  • the alkylene oxides can be used individually, alternately in succession or as a mixture.
  • the polyether acrylates can be used alone or in mixtures for the preparation of the emulsion polymers used according to the invention.
  • the emulsion polymer preferably comprises at least one polyether (meth) acrylate in copolymerized form, which is selected from compounds of the general formulas I or II or mixtures thereof
  • H 2 C CC O (CH 2 CH 2 O) n - Ra
  • H 2 C C - CO (CH 2 CH (CH 3 ) O) n - R a
  • n is an integer from 3 to 15, preferably 4 to 12,
  • R a is hydrogen, C 1 -C 20 -alkyl, C 5 -C 8 -cycloalkyl or Ce-Cu-aryl,
  • R b is hydrogen or methyl.
  • Suitable polyether (meth) acrylates are commercially available, for. In the form of various Bisomer® products from Laporte Performance Chemicals, UK. This includes z. Bisomer® MPEG 350 MA, a methoxypolyethylene glycol monomethacrylate.
  • no polyether (meth) acrylate is used in the free-radical emulsion polymerization for the preparation of the emulsion polymer.
  • At least one urea group-containing monomer is used in the free-radical emulsion polymerization for the preparation of the emulsion polymer.
  • This is preferably used in an amount of up to 25% by weight, preferably up to 20% by weight, based on the total weight of the monomers Mo).
  • 0.1 to 20% by weight, in particular 1 to 15% by weight, of at least one urea group-containing monomer is used for the emulsion polymerization.
  • Suitable urea group-containing monomers are, for. N-vinyl or N-allyl urea or derivatives of imidazolidin-2-one. These include N-vinyl- and N-allylimidazolidin-2-one, N-vinyloxyethyl-imidazolidin-2-one,
  • Preferred urea group-containing monomers are
  • N- (2-Acryloxyethyl) imidazolidin-2-one and N- (2-methacryloxyethyl) imidazolidin-2-one Particularly preferred is N- (2-methacryloxyethyl) imidazolidin-2-one (2-ureidomethacrylate, UMA).
  • no urea-containing monomer is used in the free-radical emulsion polymerization for the preparation of the emulsion polymer.
  • the abovementioned monomers Mo) can be used individually, in the form of mixtures within a monomer class or in the form of mixtures of different monomer classes. At least 40% by weight, particularly preferably at least 60% by weight, in particular at least 80% by weight, based on the total weight of the monomers Mo), of at least one monomer Mo1) which is selected from esters ⁇ are preferably used for the emulsion polymerization , ß-ethylenically unsaturated mono- and dicarboxylic acids with Ci-C2o-alkanols, vinyl aromatics, esters of vinyl alcohol with
  • the monomers Mo1 in an amount of up to 99.9 wt .-%, particularly preferably up to 99.5 wt .-%, in particular up to 99 wt .-%, based on the total weight of the monomers Mo), used for emulsion polymerization.
  • the main monomers Mo1) are preferably selected from methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate , tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, n-heptyl (meth) acrylate, n-octyl (meth) acrylate,
  • At least one further monomer Mo2) which is generally present to a lesser extent (secondary monomers) can be used in the free-radical emulsion polymerization for the preparation of the emulsion polymer.
  • at least one monomer Mo 2 which is selected are used for the emulsion polymerization ethylenically unsaturated mono- and dicarboxylic acids and the anhydrides and half-esters of ethylenically unsaturated dicarboxylic acids, (meth) acrylamides, C 1 -C 10 -hydroxyalkyl (meth) acrylates,
  • the monomers Mo2) if present, in an amount of at least 0.1 wt .-%, more preferably at least 0.5 wt .-%, in particular at least 1 wt .-%, based on the total weight of the monomers M) , used for emulsion polymerization.
  • the monomers M2) are especially selected from acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, maleic anhydride, acrylic acid amide, methacrylamide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethylacrylamide, 2-hydroxyethylmethacrylamide, and mixtures thereof.
  • Ci-Cio-alkyl (meth) acrylate and at least one vinyl aromatic, especially n-butyl acrylate, methyl methacrylate, styrene; n-butyl acrylate, styrene; n-butyl acrylate, ethylhexyl acrylate, styrene; Ethylhexyl acrylate, styrene; Ethylhexyl acrylate, methyl methacrylate, styrene;
  • the abovementioned particularly suitable monomer combinations may contain small amounts of further monomers Mo2). These are preferably selected from acrylic acid, methacrylic acid, acrylamide, methacrylamide and mixtures thereof.
  • At least one crosslinker can be used.
  • Monomers having a crosslinking function are compounds having at least two polymerizable, ethylenically unsaturated, non-conjugated double bonds in the molecule.
  • a networking can also z.
  • functional groups which can enter into a chemical crosslinking reaction with complementary functional groups.
  • the complementary groups may both be bound to the emulsion polymer, for crosslinking it is possible to use a crosslinker which is capable of undergoing a chemical crosslinking reaction with functional groups of the emulsion polymer.
  • Suitable crosslinkers are, on the one hand, those mentioned at the outset for the preparation of the polymer particles with a hydrophobic core and polyelectrolyte side chains bound thereto.
  • the crosslinking monomers include those which in addition to an ethylenically unsaturated double bond, a reactive functional group, eg. B. an aldehyde group, a keto group or an oxirane group, which with a set crosslinker can react.
  • a reactive functional group eg. B. an aldehyde group, a keto group or an oxirane group, which with a set crosslinker can react.
  • the functional groups are keto or aldehyde groups.
  • the keto or aldehyde groups are preferably bonded to the polymer by copolymerization of copolymerizable, ethylenically unsaturated compounds with keto or aldehyde groups.
  • Suitable such compounds are acrolein, methacrolein, vinyl alkyl ketones having 1 to 20, preferably 1 to 10, carbon atoms in the alkyl radical, formylstyrene, (meth) acrylic acid alkyl esters having one or two keto or aldehyde or one aldehyde and one keto group in the alkyl radical, wherein the alkyl radical preferably comprises a total of 3 to 10 carbon atoms, for.
  • B. (meth) acryloxyalkylpropanale, as described in DE-A-2722097.
  • N-oxoalkyl (meth) acrylamides as described, for.
  • the crosslinkers are preferably a compound having at least two functional groups, in particular two to five functional groups, which can enter into a crosslinking reaction with the functional groups of the polymer, especially the keto or aldehyde groups. These include z. As hydrazide, hydroxylamine or oxime ether or amino groups as functional groups for the crosslinking of the keto or aldehyde groups. Suitable compounds with hydrazide groups are, for. B.
  • hydrazide compounds having a molecular weight of up to 500 g / mol.
  • Particularly preferred hydrazide compounds are dicarboxylic acid dihydrazides having preferably 2 to 10 C atoms. These include z.
  • adipic dihydrazide, sebacic dihydrazide and isophthalic dihydrazide are Suitable compounds with hydroxylamine or oxime ether groups are, for. As mentioned in WO 93/25588.
  • a surface crosslinking can additionally be produced by appropriate addition of the aqueous polymer dispersion containing the emulsion polymer.
  • Suitable photoinitiators are those which are excited by sunlight, for example benzophenone or benzophenone derivatives.
  • Sikkativierung are the recommended for aqueous alkyd resins metal compounds, for example on the basis of Co or Mn (review in U. Poth, polyester and alkyd resins, Vincentz Network 2005, p 183 f).
  • the crosslinking component is preferably used in an amount of 0.0005 to 5 wt .-%, preferably 0.001 to 2.5 wt .-%, in particular 0.01 to 1, 5 wt .-%, based on the total weight of used for the polymerization of monomers (including the crosslinker) used.
  • a specific embodiment relates to emulsion polymers which contain no crosslinker in copolymerized form.
  • the radical polymerization of the monomer mixture M) can be carried out in the presence of at least one regulator.
  • Regulators are preferably used in an amount of 0.0005 to 5 wt .-%, particularly preferably from 0.001 to 2.5 wt .-% and in particular from 0.01 to 1, 5 wt .-%, based on the total weight of the Polymerization used monomers used.
  • Regulators are generally compounds with high transfer constants. Regulators accelerate chain transfer reactions and thus cause a reduction in the degree of polymerization of the resulting polymers without affecting the gross reaction rate. In the case of the regulators, one can distinguish between mono-, bi- or polyfunctional regulators depending on the number of functional groups in the molecule which can lead to one or more chain transfer reactions. Suitable regulators are described in detail, for example, by K.C. Berger and G. Brandrup in J. Brandrup, E.H. Immergut, Polymer Handbook, 3rd ed., John Wiley & Sons, New York, 1989, pp. 11-81-11 / 141.
  • Suitable regulators are, for example, aldehydes, such as formaldehyde, acetaldehyde, propionic aldehyde, n-butyraldehyde, isobutyraldehyde.
  • regulators formic acid, its salts or esters, such as ammonium formate, 2,5-diphenyl-1-hexene, hydroxylammonium sulfate, and hydroxylammonium phosphate.
  • halogen compounds for example, alkyl halides, such as carbon tetrachloride, chloroform, bromotrichloromethane, bromoform, allyl bromide and benzyl compounds, such as benzyl chloride or benzyl bromide.
  • alkyl halides such as carbon tetrachloride, chloroform, bromotrichloromethane, bromoform, allyl bromide
  • benzyl compounds such as benzyl chloride or benzyl bromide.
  • Suitable regulators are allyl compounds, such as. Allyl alcohol, functionalized allyl ethers such as allyl ethoxylates, alkyl allyl ethers or glycerol monoallyl ethers.
  • Compounds of this type are, for example, inorganic hydrogen sulfites, disulfites and dithionites or organic sulfides, disulfides, polysulfides, sulfoxides and sulfones. These include di-n-butyl sulfide, di-n-octyl sulfide, diphenyl sulfide, thiodiglycol, ethylthioethanol, diisopropyl disulfide, di-n-butyl disulfide, di-n-hexyl disulfide, diacetyl disulfide, diethanol sulfide, di-t-butyl trisulfide, dimethyl sulfoxide, dialkyl sulfide, Dialkyl disulfide and / or diaryl sulfide.
  • polymerization regulators are thiols (compounds which contain sulfur in the form of SH groups, also referred to as mercaptans).
  • Preferred regulators are mono-, bi- and polyfunctional mercaptans, mercaptoalcohols and / or mercaptocarboxylic acids.
  • Examples of these compounds are allyl thioglycolates, ethyl thioglycolate, cysteine, 2-mercaptoethanol, 1, 3-mercaptopropanol, 3-mercaptopropane-1, 2-diol, 1, 4-mercaptobutanol, mercaptoacetic acid, 3-mercaptopropionic acid, mercaptosuccinic acid, thioglycerol, thioacetic acid, thio urea and Al kyl mercaptans such as n-butylmercaptan, n-hexylmercaptan or n-dodecylmercaptan.
  • bifunctional regulators containing two sulfur atoms in bonded form are bifunctional thiols, such as. As dimercaptopropanesulfonic acid (sodium salt), dimercaptosuccinic acid, dimercapto-1-propanol, dimercaptoethane, dimercaptopropan, dimercaptobutane, dimercaptopentane, dimercaptohexane, ethylene glycol bis-thioglycolate and butanediol-bis-thioglycolate.
  • polyfunctional regulators are compounds containing more than two sulfur atoms in bonded form. Examples of these are trifunctional and / or tetrafunctional mercaptans.
  • controllers can be used individually or in combination with each other.
  • a specific embodiment relates to polymer dispersions Pd) which are prepared by free-radical emulsion polymerization without addition of a regulator.
  • the monomers can be polymerized with the aid of free-radical initiators.
  • the peroxo and / or azo compounds customary for this purpose can be used, as are mentioned in the preparation of the polymer particles having a hydrophobic core and polyelectrolyte side chains bonded thereto, to which reference is hereby made.
  • red / ox reduction / oxidation
  • the red / ox initiator systems consist of at least one usually inorganic reducing agent and one inorganic or organic oxidizing agent.
  • the oxidation component is z. B. to the above-mentioned initiators for emulsion polymerization.
  • the reduction components are, for. B. to alkali metal salts of sulfurous acid, such as.
  • the Red / Ox initiator systems can with the concomitant use of soluble metal compounds whose metallic component in several valence states may occur. Usual Red / Ox initiator systems are z.
  • the individual components eg. As the reduction component, may also be mixtures, for. B. a mixture of the sodium salt of hydroxymethanesulfinic acid and sodium disulfite.
  • the amount of initiators is generally 0.1 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on all monomers to be polymerized. It is also possible to use a plurality of different initiators in the emulsion polymerization.
  • the preparation of the emulsion polymers is usually carried out in the presence of at least one surface-active compound.
  • a detailed description of suitable protective colloids can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, p. 41 1 - 420.
  • Suitable emulsifiers are also found in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pp. 192-208.
  • Suitable emulsifiers are anionic, cationic and nonionic emulsifiers. Emulsifiers whose relative molecular weights are usually below those of protective colloids are preferably used as surface-active substances.
  • nonionic emulsifiers are araliphatic or aliphatic nonionic emulsifiers, for example ethoxylated mono-, di- and trialkylphenols (EO-).
  • alkyl radical C 4 -C 0
  • ethoxylates of long-chain alcohols EO units: 3 to 100
  • polyethylene oxide / polypropylene oxide homo- and copolymers may contain randomly distributed alkylene oxide or polymerized in the form of blocks.
  • Ethoxylates of long-chain alkanols (alkyl C1-C30, average degree of ethoxylation from 5 to 100), and including particularly preferably those are preferably 0 alkyl radical and a mean degree of ethoxylation of 10 to 50, and ethoxylated monoalkylphenols having a linear Ci2-C2.
  • Suitable anionic emulsifiers are, for example, alkali metal and ammonium salts of alkyl sulfates (alkyl radical: C8-C22), of sulfuric monoesters of ethoxylated alkanols (EO degree: 2 to 50, alkyl radical: Ci 2 -Ci 8 ) and ethoxylated alkylphenols (EO degree: 3 to 50, alkyl radical: C4-C9), of alkylsulfonic acids (alkyl radical: C12-C18) and of alkylarylsulfonic acids (alkyl radical: Cg-Cis).
  • alkyl sulfates alkyl radical: C8-C22
  • sulfuric monoesters of ethoxylated alkanols EO degree: 2 to 50, alkyl radical: Ci 2 -Ci 8
  • EO degree: 3 to 50 alkyl radical: C4-C9
  • alkylsulfonic acids alkyl radical:
  • emulsifiers can be found in Houben-Weyl, Methods of Organic Chemistry, Volume XIV / 1, Macromolecular Materials, Georg Thieme Verlag, Stuttgart, 1961, pp. 192-208).
  • anionic emulsifiers are also bis (phenylsulfonic acid) ethers or their alkali or ammonium salts, the one or both aromatic rings carry a C4-C24 alkyl group suitable. These compounds are well known, for. From US-A-4,269,749, and commercially available, for example as Dowfax® 2A1 (Dow Chemical Company).
  • Suitable cationic emulsifiers are preferably quaternary ammonium halides, e.g. Trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of N-C6-C20-alkylpyridines, -morpholines or -imidazoles, e.g. B. N-Laurylpyridinium chloride.
  • quaternary ammonium halides e.g. Trimethylcetylammonium chloride, methyltrioctylammonium chloride, benzyltriethylammonium chloride or quaternary compounds of N-C6-C20-alkylpyridines, -morpholines or -imidazoles, e.g. B. N-Laurylpyridinium chloride.
  • the amount of emulsifier is generally about 0.01 to 10 wt .-%, preferably 0.1 to 5 wt .-%, based on the amount of monomers to be polymerized.
  • the emulsion polymer is usually used in the form of an aqueous polymer dispersion Pd) for the preparation of the binder composition according to the invention. However, it can also be used in solid form, as obtainable by drying an aqueous polymer dispersion Pd) by conventional methods.
  • the emulsion polymers or polymer dispersions Pd) can also be added conventional auxiliaries and additives.
  • auxiliaries and additives include, for example, the pH-adjusting substances, reducing and bleaching agents, such as.
  • the alkali metal salts of hydroxymethanesulfinic acid eg Rongalit.RTM. C from BASF Aktiengesellschaft
  • complexing agents deodorants, flavoring agents, odorants and viscosity modifiers, such as alcohols, eg. As glycerol, methanol, ethanol, tert-butanol, glycol, etc.
  • These auxiliaries and additives can be added to the polymer dispersions in the template, one of the feeds or after completion of the polymerization.
  • the polymerization is generally carried out at temperatures in a range from 0 to 150 0 C, preferably 20 to 100 0 C, particularly preferably 30 to 95 0 C.
  • the polymerization is preferably carried out at normal pressure, but can also be a polymerization under elevated pressure , For example, the autogenous pressure of the components used for the polymerization.
  • the polymerization takes place in the presence of at least one inert gas, such as. As nitrogen or argon.
  • the polymerization medium can consist only of water as well as of mixtures of water and thus miscible liquids such as methanol. Preferably, only water is used.
  • the emulsion polymerization can be carried out both as a batch process and in the form of a feed process, including a stepwise or gradient procedure.
  • the feed process in which one submits a portion of the polymerization or a polymer seed, heated to the polymerization, polymerized and then the remainder of the polymerization, usually over several spatially separate feeds, of which one or more of the monomers in pure or in emulsified Contain form, continuous, stepwise or with the addition of a concentration gradient while maintaining the polymerization of the polymerization zone supplies.
  • the manner in which the initiator is added to the polymerization vessel in the course of the free radical aqueous emulsion polymerization is known to one of ordinary skill in the art. It can be introduced either completely into the polymerization vessel or continuously or in stages according to its consumption in the course of the free-radical aqueous emulsion polymerization. Specifically, this depends on the chemical nature of the initiator system as well as on the polymerization temperature in a manner known per se to those of ordinary skill in the art. Preferably, a part is initially charged and the remainder supplied according to the consumption of the polymerization.
  • the dispersions formed during the polymerization can be subjected to a physical or chemical aftertreatment following the polymerization process.
  • Such methods are, for example, the known methods for residual monomer reduction, such as.
  • the post-treatment by addition of polymerization initiators or mixtures of polymerization initiators at appropriate temperatures, an aftertreatment of the polymer solution by steam or ammonia vapor or stripping with inert gas or treating the reaction mixture with oxidizing or reducing reagents, adsorption as the adsorption of impurities on selected media such , As activated carbon or ultrafiltration.
  • the obtained aqueous polymer dispersion Pd) usually has a solids content of 20 to 70 wt .-%, preferably 40 to 70 wt .-%, particularly preferably 45 to 70 wt .-% and particularly preferably from 45 to 65 wt .-%, based on the polymer dispersion.
  • the titanium dioxide compositions used according to the invention are distinguished by good compatibility with a multiplicity of different dispersions.
  • the binder compositions of the invention can be used in aqueous coating compositions, such.
  • Suitable further polymers are z. B. film-forming polymers. These include z. B. alkyd resins.
  • Suitable alkyd resins are, for. B. water-soluble alkyd resins, which preferably have a weight-average molecular weight of 5000 to 40,000. Also suitable are alkyd resins having a weight-average molecular weight of more than 40,000, especially more than 100,000.
  • An alkyd resin is understood to mean a polyester which is esterified with a drying oil, a fatty acid or the like (U. Poth, polyester and alkyd resins, Vincentz Network 2005).
  • Suitable water-soluble alkyd resins are alkyd resins having a sufficiently high acid number, preferably in the range of 30 to 65 mg KOH / g. These may optionally be partially or completely neutralized.
  • the weight-average molecular weight is preferably 8,000 to 35,000, and more preferably 10,000 to 35,000.
  • a specific embodiment is therefore a coating agent which does not have a film-forming polymer other than the emulsion polymer.
  • the binder compositions according to the invention are preferably used in aqueous paints. These paints are pigmented systems because of their TiO 2 content. This could have additional additional pigments different from TiO.sub.2.
  • the proportion of pigments can be described by the pigment volume concentration (PVK).
  • paints can be classified using the PVK as follows:
  • Exterior facade color white approx. 45 - 55%
  • Another object of the invention is therefore a paint in the form of an aqueous composition containing
  • binder composition as defined above, if appropriate at least one pigment other than titanium dioxide, optionally at least one filler, optionally further auxiliaries other than pigments and fillers, and
  • a preferred embodiment is a paint in the form of an emulsion paint.
  • Preferred is a paint containing: 10 to 60% by weight, based on the solids content of at least one binder composition, as defined above,
  • Emulsion paints generally contain from 30 to 75% by weight, and preferably from 40 to 65% by weight, of non-volatile constituents. This is to be understood as meaning all constituents of the preparation which are not water, but at least the total amount of binder, filler, pigment, low-volatile solvents (boiling point above 220 ° C.), eg. As plasticizers, and polymeric adjuvants. This accounts for about
  • pigments and fillers eg. As color pigments, white pigments and inorganic fillers. These include inorganic white pigments such as barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopone (zinc sulfide + barium sulfate) or colored pigments, for example iron oxides, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese black, antimony black, manganese violet, Paris blue or Schweinfurter green contain. In addition to the inorganic pigments, the emulsion paints of the invention may also organic color pigments, for.
  • inorganic white pigments such as barium sulfate, zinc oxide, zinc sulfide, basic lead carbonate, antimony trioxide, lithopone (zinc sulfide + barium sulfate) or colored pigments, for example iron oxides, carbon black, graphite, zinc yellow, zinc green, ultramarine, manganese
  • Suitable fillers are for.
  • aluminosilicates such as feldspars, silicates, such as kaolin, talc, mica, magnesite, alkaline earth metal carbonates, such as calcium carbonate, for example in the form of calcite or chalk, magnesium carbonate, dolomite, alkaline earth sulfates, such as calcium sulfate, silica, etc.
  • the fillers can be used as individual components. In practice, however, filler mixtures have proven particularly useful, for. Calcium carbonate / kaolin, calcium carbonate / talc. Glossy paints generally have only small amounts of very finely divided fillers. Finely divided fillers can also be used to increase the hiding power and / or to save on white pigments. To adjust the hiding power of the hue and the depth of shade, blends of color pigments and fillers are preferably used.
  • the paint according to the invention may contain further auxiliaries.
  • auxiliaries include, in addition to the emulsifiers used in the polymerization, wetting agents or dispersants, such as sodium, potassium or ammonium polyphosphates, alkali metal and ammonium salts of acrylic or maleic anhydride copolymers, polyphosphonates, such as 1-hydroxyethane-1, 1 diphosphonic acid sodium and Naphthalinsulfonklaresalze, especially their sodium salts.
  • auxiliaries are leveling agents, defoamers, biocides and thickeners.
  • Suitable thickeners are z.
  • Associative thickener such as polyurethane thickener.
  • the amount of thickener is preferably less than 1 wt .-%, more preferably less than 0.6 wt .-% thickener, based on the solids content of the paint.
  • the preparation of the paint according to the invention is carried out in a known manner by mixing the components in mixing devices customary for this purpose. It has proven useful to prepare an aqueous paste or dispersion from the pigments, water and optionally the auxiliaries, and then first the polymeric binder, ie. H. as a rule, to mix the aqueous dispersion of the polymer with the pigment paste or pigment dispersion.
  • the paints according to the invention generally contain from 30 to 75% by weight and preferably from 40 to 65% by weight of nonvolatile constituents. This is to be understood as meaning all constituents of the preparation which are not water, but at least the
  • the volatile constituents are predominantly water.
  • Suitable paints are also glossy paints. The determination of the
  • Gloss of the paint can be done according to DIN 67530.
  • the coating material with a gap width of 240 ⁇ m is applied to a glass plate and dried for 72 hours at room temperature.
  • the specimen is placed in a calibrated reflectometer and, at a defined angle of incidence, the extent to which the returned light has been reflected or scattered is determined.
  • the determined reflectometer value is a measure of the gloss (the higher the value, the higher the gloss).
  • the paint of the invention can be applied in a conventional manner to substrates, for. B. by brushing, spraying, dipping, rolling, knife coating, etc.
  • It is preferably used as a decorative paint, i. H. used for coating buildings or parts of buildings. It may be mineral substrates such as plasters, gypsum or plasterboard, masonry or concrete, wood, wood materials, metal or paper, z. B. wallpaper or plastic, z. As PVC, act.
  • the paint for building interior parts z.
  • interior walls, interior doors, wainscoting, banisters, furniture, etc. use.
  • the paints of the invention are characterized by easy handling, good processing properties and high hiding power.
  • the paints are low in emissions. They have good performance properties, eg. B. a good water resistance, good wet adhesion, especially on alkyd paints, good blocking resistance, good paintability, and they show a good course when applied.
  • the tool used can be easily cleaned with water.
  • binder compositions according to the invention are also particularly suitable for use as binders in paper coating slips.
  • Emulsion polymers according to the invention for use in paper coating slips preferably comprise an emulsion polymer which comprises in copolymerized form at least one monomer Mo) or a monomer combination which is selected from:
  • a special embodiment of the emulsion polymer are polybutadiene binders which contain in copolymerized form butadiene and a vinylaromatic, in particular styrene, and optionally at least one further monomer.
  • the weight ratio of butadiene to vinyl aromatic is z. From 10:90 to 90:10, preferably from 20:80 to 80:20.
  • Polybutadiene binders are particularly preferred, the emulsion polymer being at least 40% by weight, preferably at least 60% by weight, particularly preferred at least 80 wt .-%, in particular at least 90 wt .-% of hydrocarbons having two double bonds, in particular butadiene, or mixtures of such hydrocarbons with vinyl aromatics, in particular styrene consists.
  • Binders which contain at least one C 1 -C 10 -alkyl (meth) acrylate or a mixture of at least one C 1 -C 10 -alkyl (meth) acrylate and at least one vinylaromatic (in particular styrene) in copolymerized form.
  • the emulsion polymers contained in the polybutadiene binders and the polyacrylate binders may contain other monomers, for.
  • monomers with carboxylic acid sulfonic acid or phosphonic acid groups.
  • the emulsion polymers contain at least one ethylenically unsaturated acid in an amount of 0.05 wt .-% to 5 wt .-%, based on the total weight of the monomers used, in copolymerized form.
  • hydroxyl-containing monomers in particular Ci-Cio-hydroxyalkyl (meth) acrylates, or amides such as (meth) acrylamide.
  • Ingredients include paper coating slips in particular
  • a fluorescent or phosphorescent dye in particular as an optical brightener
  • auxiliaries for.
  • binder As further binders z. As well as natural polymers, such as starch, to be used.
  • the proportion of binder according to the invention is preferably at least 50% by weight, particularly preferably at least 70% by weight or 100% by weight, based on the total amount of binder.
  • the paper coating slips preferably comprise binders in amounts of from 1 to 50 parts by weight, more preferably from 5 to 20 parts by weight, of binder, based on 100 parts by weight of pigment.
  • Suitable thickeners b), in addition to synthetic polymers, are, in particular, cellulose, preferably carboxymethyl cellulose.
  • pigment d is understood here as inorganic solids. These solids are responsible as pigments for the color of the paper coating slip (especially white) and / or have only the function of an inert filler.
  • the pigment is generally white pigments, e.g. As barium sulfate, calcium carbonate, calcium sulfoaluminate, kaolin, talc, zinc oxide, chalk or coating Clay or silicates.
  • the preparation of the paper coating slip can be done by conventional methods.
  • the paper coating slips according to the invention are well suited for the coating of z. B. raw paper or cardboard.
  • the coating and subsequent drying can be carried out by customary methods.
  • the coated papers or cardboard have good performance properties, in particular, they are also good in the known printing processes, such as flexographic, letterpress, gravure or offset printable. Especially in the offset process they produce a high pick resistance and a fast and good color and water acceptance.
  • the papers coated with the paper coating slips can be used well in all printing processes, in particular in offset printing.
  • Methacrylic acid 2- [4- (2-hydroxy-2-methyl-propionyl) -phenoxy] -ethylester was prepared by reacting methacrylic acid chloride with Irgacure® 2959 (4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-) propyl) ketone, available from Ciba Spezialitätenchemie, Switzerland) according to the method of Guo, X., Weiss, A. and Baulstrom, M., Macromolecules, 1999, 32, pp. 6043-6046.
  • Sodium 4- styrenesulfonate is available, for example, from Aldrich.
  • the photoemulsion polymerization was carried out in a UV reactor (Heraeus TQ 150 Z3, wavelength range 200 to 600 nm).
  • Low temperature transmission electron microscopy (cryo-TEM) was performed as described by Li, Z., Kesselman, E., Talmon, Y., Hillmyer, MA, Lodge, TP, Science 306, p. 98-101, (2004).
  • FE-SEM Field Emission Scanning Electron Microscopy
  • the UV spectra were recorded on a Lambda 25 spectrometer from Perkin Elmer.
  • the X-ray diffraction experiments (XRD) were performed at 25 0 C on a Panalytical XPERT-PRO diffractometer in reflection mode using Cu Ka radiation.
  • Example 1 TiO 2 nanocomposite particles
  • copolymers of polystyrene and HMEM were prepared by processes known from the literature (Ballauff, M., Spherical polyelectrolyte brushes, Moscow Polym., Vol. 32, pp. 1135-1151 (2007).
  • the dispersion obtained in 1.1.1 was diluted to 2.5% solids with water.
  • Sodium-4-styrenesulfonate (30 mol%, based on styrene) was then added with stirring.
  • the sealed reactor was evacuated several times and purged with nitrogen.
  • the photoemulsion polymerization was started by irradiating the reactor with UV light. It was irradiated for 60 minutes at room temperature (25 0 C).
  • the reaction mixture was purified by dialysis against purified water (membrane: cellulose nitrate with 100 nm pore size, Fa. Schleicher & Schuell). Then, by dialysis, water was exchanged for ethanol (membrane: regenerated cellulose with 200 nm pore width, Schleicher & Schuell).
  • PS-NaSS polystyrene cores with polyelectrolyte side chains from 1.1.2 (solids content is 4.62% by weight)
  • FIG. 1e is a cryo-TEM image for TiO 2 composite particles of sample B.
  • TiO2 nanocomposite particles of Sample A (lower water content approach) have a diameter of 4 ⁇ 1.5 nm.
  • Sample B (higher water content fraction) TiO 2 nanocomposite particles have a diameter of 12 ⁇ 2 nm ( determined from TEM image, FIGS. 1 c and 1 d).
  • Titanium dioxide content
  • TiO 2 content of the TiO 2 nanocomposites was determined by thermogravimetry (TGA) with a Mettler Toledo STARe instrument. After drying the sample in vacuo at 30 0 C overnight, the Ti ⁇ 2 composite particles were at 800 0 C at a heating rate heated at 10 ° C / min in argon or air. TGA analysis showed a weight fraction of 19.8% TiO 2 .
  • FIG. 3 shows an HRTEM image of the TiO 2 nanocomposite on which the crystal lattice on the polystyrene core can be seen.
  • Grating rings with a lattice spacing of approximately 0.35 nm refer to the (101) planes of anatase TiO 2.
  • SAED diffraction pattern
  • Nanokompositproben were heated in a Thermolyserohr two hours in air at 500 0 C, to decompose the polystyrene cores with Polyelektrolytrichketten. Highly porous TiO 2 was obtained.
  • the obtained TiO 2 in 1.2 Nanokompositproben were serohr in a thermolysis initially under an argon atmosphere for two hours 500 0 C is heated to decompose the polymer to carbon. Then, the carbon skeleton was removed by heating the material in air to 500 ° C. over a period of two hours. In this way a highly porous framework of TiO 2 was obtained.
  • FIG. 4 is an EDX measurement for sample B after the calcination process.
  • the EDX measurement (energy disperse X-ray) proves that the organic polymer had completely decomposed by the calcination and only TiO 2 remained.
  • FIGS. 5a and 5b are FE-SEM images of a thin layer of polystyrene cores with polyelectrolyte side chains, TiO 2 composite particles on Si wafers after calcining directly in air (a) or first in argon and then in air (b).
  • Figure 5c shows N2 adsorption-desorption isotherms for the air-calcined TiO 2 nanomaterials produced here (c).
  • FIG. 5 a shows the macropores of mesoporous OO 2 after the heat treatment.
  • the macropores are due to the polystyrene core, the mesopores to the Polyelektrolytrichketten.
  • the mesopores have a diameter of 12.3 nm (calculated by BET analysis, see Figure 5c). This is associated with an increase in surface area from 34.61 m 2 / g (before calcination) to 64.25 m 2 / g (after calcination).
  • Figures 5d, 5e and 5f are FE-SEM images of bulk samples after calcination under argon atmosphere (5d, 5e) and then in air (5f).
  • Figures 5d and 5e show the formation of mesoporous structures in which carbon forms the pore walls in which TiO 2 nanoparticles are homogeneously embedded. After heating in the presence of air, white TiO 2 nanomaterials having a highly porous structure were obtained (FIG. 5 f). In addition, TiO 2 nanoparticles with a diameter of approx. 12 nm can be seen on this picture.
  • the photocatalytic activity of the TiO 2 composite particles was investigated by decolorization of rhodamine B (RhB) solutions.
  • Ct is the concentration of RhB at time t
  • ki is the rate constant normalized to S
  • the surface of the Ti ⁇ 2 nanoparticles normalizes to the unit volume of the system.
  • the density p 3.90x10 3 kg / m 3 was used as the density for anatase TiO 2.
  • the values for the apparent rate constant k a pp increase linearly with increasing specific surface area of the TiO 2 nanocomposite particles.
  • Figure 7 shows the rate constant kapp as a function of the surface S of sample B normalized to the unit volume of the system.
  • Table 2 shows the photocatalytic activity of the TiO 2 nanoparticles for the degradation of RhB.
  • V1 comparative sample Li, J., Ma, W., Chen, C, Zhao, J., Zhu, H., Gao, X., Photodegradation of dye pollutants on one-dimensional TiO 2 nanoparticles under UV and visible irradiation, J. Mol. Catal. AQQ, 131-138 (2007).

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Abstract

La présente invention porte sur une composition de dioxyde de titane contenant des nanoparticules de dioxyde de titane, sa préparation et son utilisation.
EP09757507A 2008-06-03 2009-06-02 Composition de dioxyde de titane contenant des nanoparticules de dioxyde de titane, sa préparation et son utilisation Withdrawn EP2288577A1 (fr)

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EP09757507A EP2288577A1 (fr) 2008-06-03 2009-06-02 Composition de dioxyde de titane contenant des nanoparticules de dioxyde de titane, sa préparation et son utilisation

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CN108398733B (zh) * 2018-03-08 2019-09-27 常熟理工学院 一种二氧化钛/二氧化硅一维光子晶体及其制备方法
CN111790418B (zh) * 2019-04-08 2023-05-26 国家纳米科学中心 一种钙钛复合材料及其制备方法和用途
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CN102056843A (zh) 2011-05-11
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