EP1984302A1 - Procede de fabrication de nanoparticules de molybdate de lithium - Google Patents
Procede de fabrication de nanoparticules de molybdate de lithiumInfo
- Publication number
- EP1984302A1 EP1984302A1 EP07702880A EP07702880A EP1984302A1 EP 1984302 A1 EP1984302 A1 EP 1984302A1 EP 07702880 A EP07702880 A EP 07702880A EP 07702880 A EP07702880 A EP 07702880A EP 1984302 A1 EP1984302 A1 EP 1984302A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- water
- particles
- soluble compounds
- nanoparticulate
- dispersible particles
- 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- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
-
- 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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/04—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Definitions
- the present invention relates to novel molybdate nanoparticles, a process for the preparation of nanoparticles by recrystallization or recrystallization and their use.
- Molybdate especially lithium molybdate, are of great interest as catalysts for accelerating the reaction of aqueous 2K-PUR applications because they contribute to the acceleration of the reaction but do not affect the pot life of the system.
- Alkalimetallmolybdate are water-soluble, so they can therefore typically be introduced directly into the aqueous 2K-PUR formulations.
- a direct incorporation into an anhydrous component or composition such as the isocyanate component is not readily possible, since the alkali metal molybdate are usually coarsely crystalline and not or hardly soluble in the organic medium and thus a homogeneous incorporation is not given.
- the free NCO groups would react with the water of an aqueous solution of molybdate, which is also undesirable.
- nanoparticulate dispersible molybdate particles which have an average particle size of less than 500 nm. These are available through a special manufacturing process.
- the invention relates to nanoparticle-dispersible particles of water-soluble compounds having an average particle size of less than 500 nm, preferably less than 150 nm, particularly preferably 2 to 60 nm.
- the particle sizes given in the context of the present invention were determined according to Khrenov et al. (2005, Macromolecular Chemistry and Physics 206, p. 96ff) by means of dynamic light scattering in particle number weighting.
- Water-soluble compounds for the preparation of the particles according to the invention may be all inorganic or organic compounds which are known to the person skilled in the art and have a solubility in water.
- metal salts such as preferably molybdates are suitable.
- Molybdenum data refers to the salts of molybdic acid H 2 MoO 4 and their polyacids, which are obtained by reacting the acids with bases. Be alkali metal or Alkaline earth metal hydroxides used as bases, alkali metal or Erdalkalimetallmolybda- te are obtained.
- lithium, sodium and zinc molybdate are preferred as molybdate.
- Particularly preferred nanoparticulate dispersible particles of the type according to the invention are lithium molybdate particles having an average particle size of from 5 to 60 nm.
- the particles are crystalline or amorphous.
- Another object of the present invention is a process for the preparation of nanoparticulate dispersible particles of water-soluble compounds having an average particle size of less than 500 nm, in which a water-in-oil emulsion of
- the water contained is removed up to a residual content of at most 2 wt .-% based on the final product.
- an aqueous solution of a water-soluble compound is understood as meaning a homogeneous solution of the relevant compound at the relevant temperature in water as solvent, the compound being completely dissolved therein and no solid matter being precipitated in the solution.
- aqueous solutions may contain up to 5% by weight of a solvent other than water. Preferably, they contain only water as a solvent.
- the composition of the mixture before step D) is 1 to 20% by weight of water, 50 to 98.8% by weight of organic solvent, 0.005 to 10% by weight of compound to be precipitated in the form of nanoparticles and 0, 1 to 20 wt .-% stabilizer.
- the composition of the mixture prior to step D) is 2 to 10% by weight of water, 79 to 97% by weight of organic solvent, 0.01 to 1% by weight of compound to be precipitated in the form of nanoparticles and 0.1 to 10 wt .-% stabilizer.
- the emulsion which forms when the components A) to C) are mixed contains swollen micelles or drops of the compound dissolved in water in the organic solvent as the continuous phase, these micelles or drops being stabilized by the stabilizer C).
- the micelle or droplet sizes measured by TEM (after freeze-etching and carbon coating), dynamic light scattering or laser diffraction are typically 10 nm to 50,000 nm, preferably 10 nm to 5000 nm, particularly preferably 10 to 500 nm, very particularly preferably 10 nm to 100 nm. In the latter case one speaks of so-called microemulsions.
- Microemulsions are generally characterized by a high transparency due to droplet sizes of less than 100 nm and low interfacial energies of less than 0.1 mN / m. In the presence of aqueous-dissolved salts and polymeric additives, the transparency may decrease and the interfacial energy may increase, yet the emulsions spontaneously form; they are thermodynamically favored systems. Microemulsions which are self-dispersing after simple mixing of components A) to C) and gentle shaking were preferably used in the process according to the invention.
- desalted water having a conductivity of less than 5 ⁇ S / cm is preferably used.
- Molybdate salts preferably lithium, sodium or zinc molybdate, particularly preferably lithium molybdate, are particularly preferably used in A).
- the solutions used in A) typically have concentrations of the relevant dissolved compound of 0.01 to 40 wt .-%, preferably 0.1 to 30 wt .-%, particularly preferably 0.5 to 20 wt .-%.
- B) it is possible to use all customary organic solvents which are immiscible with water indefinitely and can thus form a two-phase mixture with water.
- These are, for example, octane, decane, dodecane, halogenated hydrocarbons such as 1, 2-dichloroethane, aromatic solvents such as toluene, xylene, Solvesso (trademark of Exxon Mobil, Huston, USA) and ether and / or ester group-containing compounds.
- B) butyl acetate, methoxypropyl acetate, ethyl acetate, caprolactone, solvesso, toluene, xylene or mixtures thereof are preferably used in B). Particularly preferred is butyl acetate.
- the solvent used in B) is previously saturated with water, that is, it is the organic solvent or solvent mixture so much water is added until forms a two-phase mixture at the prevailing temperature. The supernatant is then saturated with water and can be used in B).
- Suitable stabilizers C) are nonionic surfactants, anionic surfactants and cationic surfactants, as well as block copolymers or polyelectrolytes.
- cosurfactants such as alkanols with carbon chains C r Cio may be required.
- Preferred stabilizers are polymers, more preferably block copolymers which according to Foerster and Antonietti (Foerster, S. & Antonietti, M., Advanced Materials, 10, no. 3, (1998) 195) have a solvate block for the interaction with the solvent and a functional group Wear block for interaction with the particle surface.
- Solvate blocks differ in their hydrophilicity / hydrophobicity and can be poly (styrenesulfonic acid) (PSSH), poly (N-alkylvinylpyridinium halide) (PQ2VP, PQ4VP), poly (methacrylic acid) (PMAc, PAAc), poly (methacrylate) (PMA ), Poly (N-vinylpyrrolidone) (PVP), poly (hydroxyethyl methacrylate) (PHEMA), poly (vinyl ether) (PVE), poly (ethylene oxide) (PEO), poly (propylene oxide) (PPO), poly (vinyl methyl ethers) (PVME), poly (vinyl butyl ether) (PVBE), polystyrene (PS), poly (ethylenepropylene) (PEP), poly (ethylethylene) (PEE), poly (isobutylene) (PEP), poly (dimethylsiloxane) (PDMS), partially fluorin
- Functional blocks are characterized by the ability to interact specifically with the particle surfaces to be formed. Such interactions may be of the type of ligand, acid-base, electrostatic, complex, low-energy interactions, such as poly (N-alkylvinylpyridinium halide) (PQ2VP, PQ4VP), poly (dimethylsiloxane) (PDMS), partially fluorinated blocks ( PF), poly (ethylene oxide) (PEO), specific ligand-containing blocks (PL, for example, mercapto-containing blocks for metal-mercapto interactions, etc.), poly (methacrylic acid) (PMAc), poly (styrenesulfonic acid) (PSSH) , Poly (cyclopentadienylmethyl) norbomene) (PCp, eg, interactions with transition metals via metallocene complexation), poly (aminoacid) blocks (PA, eg site-specific drug delivery, biomineralization).
- PQ2VP poly (N-alkylvinylpyr
- PEO-PPO-PEO or PPO-PEO-PPO block copolymers are particularly preferred for the process according to the invention.
- PEG-nBA polyoxyalkylene amines
- PEG-nBA polyoxyalkylene amines
- the components A) to C) can be mixed in any order, preferably the stabilizers of component B) are added before A) and B) are mixed together.
- the mixing of the aqueous and the organic phase is carried out with stirring or by supplying increased energy, for example by high-pressure homogenization, rotor-stator systems, Turrax, ultrasound, magnetic stirrers or other dispersing methods, preferably with stirring by means of conventional stirrers, such as magnetic stirrers or rotor-stator systems.
- the process is preferably carried out at temperatures of from 0 ° C. to 150 ° C., more preferably from 0 ° C. to 80 ° C., very particularly preferably from 20 to 60 ° C.
- step D The water still remaining in the system after mixing A) to C) must be removed by step D).
- Suitable for this purpose are the addition of desiccant, distillative methods, increasing the solubility of water in the organic phase by polar solvent additives, spray drying or freeze drying.
- the water is preferably removed by means of drying agents corresponding to the solvent, such as silica gel or by distillation.
- the residual content of water in the resulting stable dispersions of the particles according to the invention is preferably less than 1% by weight, more preferably less than 0.5% by weight.
- the particles obtainable according to the invention have the abovementioned average particle sizes, with less than 10%, preferably less than 5%, particularly preferably less than 1%, of the particles having sizes of more than 500 nm, preferably more than 350 nm, particularly preferably more than 200 nm exhibit.
- the size distributions were calculated according to Khrenov et al. (2005, Macromolecular Chemistry and Physics 206, p. 96ff) by means of dynamic light scattering in particle number weighting and transmission electron microscopy via image evaluation.
- Such coarse particles can arise inter alia by irreversible agglomeration in the preparation of gels or powders and are therefore undesirable because the fineness of the dispersions prepared from such particles suffers and makes homogeneous incorporation difficult. Such particles are therefore referred to as coarse fraction. If necessary, small amounts of coarse fraction can be filtered off.
- Such dispersions may even be long term stable, i. There is no solid deposition even after months of storage. If solid deposits do occur, they can be removed by simply shaking or stirring the storage vessel, with the deposited particles returning to the disperse phase. Deposition of hard constituents or gel particles that are not redispersible again does not occur.
- the preparation according to the invention has the advantage that it is a type of recrystallization or recrystallization of the salt in question, the desired nanoparticles being obtained by-product-free and no further work-up steps, such as removal of salts, being necessary after removal of the water.
- Another object is therefore dispersions containing the water-soluble particles according to the invention, preferably molybdate particles having an average particle size of less than 500 nm.
- These dispersions typically have solids contents of 0.001 to 50 wt .-%, preferably 0.002 to 20 wt .-%, more preferably, 0.005 to 5 wt .-%, most preferably 0.01 to 1 wt .-%.
- the particles of the invention may also be obtained as redispersible gels or powders by complete separation of solvent and water by distillation or filtration.
- These gels or powders typically have solids contents of from 0.1 to 75% by weight, preferably from 0.5 to 50% by weight, particularly preferably from 0.5 to 35% by weight, of the nanoparticulate salt in stabilizer matrix.
- the residual content of water and organic solvent is typically less than 5 wt .-%, preferably less than 1 wt .-% based on the obtained powder or gel.
- the particles according to the invention preferably in the form of dispersions in organic media, can be dispersed in hydrophobic media such as, for example, isocyanates, whereby stable dispersions of these particles in the particular isocyanate can be obtained.
- hydrophobic media such as, for example, isocyanates
- the molybdate particles according to the invention and their dispersions are particularly suitable as catalysts for aqueous polyurethane applications.
- a further subject of the invention is the use of the molybdate particles according to the invention as catalysts for aqueous 2K PU applications.
- component A In addition to molybdate salts, other water-soluble compounds which fulfill the above criteria of the salts of component A) can also be used in component A).
- Examples are sodium chloride, silver nitrate, sodium glutamate, water-soluble therapeutic agents such as polypeptides, polysaccharides or polynucleotides, water-soluble corrosion inhibitors such as chromates, flame retardant additives such as polyphosphates, phosphonates, aluminum hydroxide, silica, water-soluble organic redox and pH indicators.
- water-soluble therapeutic agents such as polypeptides, polysaccharides or polynucleotides
- water-soluble corrosion inhibitors such as chromates
- flame retardant additives such as polyphosphates, phosphonates, aluminum hydroxide, silica, water-soluble organic redox and pH indicators.
- water-soluble therapeutic agents such as polypeptides, polysaccharides or polynucleotides, which otherwise show poor bioavailability (see US20030138557).
- the active ingredients can be protected from premature dissolution in water, transported selectively via organic media (inter alia through biological membranes) and can be incorporated into cells by nanoscale.
- water-soluble, therapeutically active proteins examples include peptides, polynucleotides, anti-coagulants, anti-cancer drugs, diabetes drugs, antibiotics, and the like. are listed in US20030138557.
- ⁇ Polar, inorganic silica particles can be precipitated by the process essential to the invention.
- PEO-PPO-PEO block copolymer BASF, Ludwigshafen, Germany: Pluronic PEI 0500, Pluronic P123, Pluronic PE 6120; PPO-PEO-PPO block copolymers (BASF, Ludwigshafen, Germany): Pluronic RPE 1740, Pluronic RPE 1720; PMMA-PEO block copolymer (Goldschmidt, Essen, Germany): Tegomer ME1010 (from Tego GmbH, Essen, Germany); Nonionic surfactant Brij 30 (PEO- (4) -lauryl alcohol, from Fluka Chemie AG, Buchs, Switzerland); Amine surfactant Genamin TI 50 (EO- (2) tallow fatty amine, Clariant, Gendorf, Germany),
- PEO-PPO-PEO block copolymers (OH end-functional):
- PPO-PEO-PPO block copolymers (OH end-functional):
- Desmodur ® N3300 hexamethylene diisocyanate trimer, which is hydrophilized by a polyether, NCO content 21.8 wt .-%, viscosity at 23 ° C 2500 mPas, Bayer Materials- cience AG, Leverkusen, DE.
- Bayhydur ® 3100 hexamethylene diisocyanate trimer, which is hydrophilized by a polyether, NCO content 17.4 wt .-%, 2800 mPas, Bayer MaterialScience AG, Leverkusen, DE.
- Bayhydur XP2487 ® anionically hydrophilicized polyisocyanate, NCO content 20.6 wt .-%, viscosity at 23 ° C 5400 mPas, Bayer MaterialScience AG, Leverkusen, DE.
- Bayhydur ® VP LS 2319 hexamethylene diisocyanate trimer, which is hydrophilized by a polyether, NCO content 18.0 wt .-% Viscosity at 23 0 C of 4,500 mPas, Bayer Materials- cience AG, Leverkusen, DE.
- Bayhydur LPLAS 5642 anionically hydrophilicized polyisocyanate, NCO content 20.6% by weight, viscosity at 23 ° C. 3500 mPas, Bayer MaterialScience AG, Leverkusen, DE.
- Example 1 Preparation of microemulsions of water, butyl acetate and stabilizer
- Each 50 ⁇ L of water was dispersed in 5 mL of water-saturated butyl acetate.
- the dispersion was carried out using a Branson 250D ultrasonic disintegrator (3 mm tip, two times 30 sec., 17% amplitude) with ice cooling. Type and content of surfactant or block copolymer were varied.
- An indication of microemulsions resulted from visually determined, optical transparency or from high transmission values (> 90%) and low interfacial tensions ( ⁇ 1 mN / m) of the emulsions.
- Transparent microemulsions were obtained in the following ternary mixtures and ratios of water / butyl acetate / stabilizer (W / O / S in parts by weight w / w / w):
- a transparent 2% by volume water-in-oil microemulsion of aqueous lithium molybdate solution in butyl acetate was prepared by adding 0.5 ml of a 2% w / w aqueous lithium molybdate solution to 25 ml of butyl acetate in the presence of 13.2 g Pluronic P123 / L emulsion obtained.
- the salt content of the emulsion was 390 ppm, the water-surfactant ratio was 1.32 mL aqueous lithium molybdate solution (2% by weight) per gram of Pluronic P 123.
- Example 2 The clear emulsions from Example 1 were adjusted with appropriate surfactant or block copolymer with aqueous lithium molybdate solution (0.05, 0.5 or 5% w / w lithium molybdate / water) and the water by means of silica gel (Bohlender GmbH, Dry pearls orange) withdrawn. For the removal of water, approximately 1.2 g of silica gel beads were used for each 5 mL batch. Particle size measurements were then performed by dynamic light scattering (Brookhaven BIC90, log-normal weighted particle count) after filtration through a 0.45 ⁇ m syringe filter (Millipore, Millix HV).
- aqueous lithium molybdate solution 0.05, 0.5 or 5% w / w lithium molybdate / water
- silica gel Bohlender GmbH, Dry pearls orange
- a dispersion of 2750 ppm nanoparticulate lithium molybdate in butyl acetate was prepared as follows. 6 mL of butyl acetate with 50 g / L of Pluronic PEI 0500 were admixed with 290 ⁇ L of 5% by weight aqueous lithium molybdate solution. The emulsion was shaken and heated to 80 ° C. three times and cooled again at RT. The addition of about 1.5 g of silica gel beads for dehydration was carried out at 8O 0 C on the last heating. After 10 minutes, the supernatant dehydrated dispersion was removed from the desiccant.
- a dispersion of 14390 ppm nanoparticulate lithium molybdate in butyl acetate was prepared as follows. 10 mL butyl acetate with 50 g / L Pluronic PEI 0500 were mixed with 633 .mu.l 20 wt .-% aqueous lithium molybdate solution and further processed according to Example 4. Particle size measurements were by dynamic light scattering (Brookhaven, BIC 90). Particle-weighted log-normal analysis revealed particle sizes of 101 nra.
- a dispersion of 1436 ppm nanoparticulate lithium molybdate in butyl acetate was prepared as follows. 25 mL butyl acetate with 50 g / L Pluronic PEI 0500 were mixed with 1580 ⁇ L 2 wt .-% aqueous lithium molybdate solution. The emulsion was shaken briefly and heated twice to approx. 60 ° C. and cooled again at RT. The water was removed at 40 0 C and about 30 mbar in a rotary evaporator and the volume was reduced to about one third. Water contents according to Karl Fischer (DIN-ISO 17025) were ⁇ 0.5 wt .-%.
- Particle size measurements were by dynamic light scattering (Brookhaven, BIC 90). From particle number-weighted log-normal evaluation, particle sizes of 110 nm (measured undiluted) and 54 nm (after dilution in butyl acetate by filling to 25 ml starting volume) were obtained.
- stock dispersions A and B were prepared according to Example 6.
- stock dispersion A was prepared at a concentration of 1400 ppm lithium molybdate in butyl acetate and dewatered by means of a rotary evaporator at 40 ° C. and about 30 mbar.
- Stock dispersion B was prepared at a concentration of 1000 ppm of lithium molybdate in butyl acetate and dewatered by means of a rotary evaporator at 40 ° C. and about 30 mbar and subsequently by the addition of silica gel (12 g, 15 min reaction time).
- the water contents according to Karl Fischer (DIN-ISO 17025) were ⁇ 0.5 wt .-%.
- each of the parent dispersions A and B was added to 4.5 g of isocyanate and homogenized by means of Vortex homogenizer (EKA, MS 2) at RT. After 1 week, the transmissions were measured using a photometer (Dr. Lange Digital Photometer LP 1 W, 1 cm cuvette diameter, 650 nm) and the particle sizes were measured by means of DLS (Brookhaven, BIC 90) and the particle diameter was determined (lognormal representation, particle number weighting). The particle size measurements were made from 10-fold dilutions of the isocyanate / lithium molybdate dispersions in butyl acetate after 30 minutes of ultrasonic bath treatment.
- Vortex homogenizer EKA, MS 2
- Example 6 a microemulsion in the ratio W / O / S of 1.26 / 17.8 / 1 was prepared.
- 25 mL butyl acetate were mixed with 1.25 g Pluronic PE 10500 (50 g / l) and 1.58 mL 2% by weight aqueous lithium molybdate solution in a 50 mL graduated cylinder, heated twice at 70 ° C. for 2 min in a water bath and shaken by hand.
- the water was removed at 40 ° C. and ⁇ 30 mbar in a rotary evaporator, the dispersion was concentrated to about 8 ml and transferred by pipette to a 50 ml measuring cylinder.
- Air Products 1) Air Products NL, additive to improve flow, substrate wetting, defoaming;
- Bayhydrol ® Al 45 Water-soluble, OH-functional polyacrylate dispersion, about 45% in water / solvent naphtha 100/2-butoxyethanol, neutralized with dimethylethanolamine, about 45.6: 4: 4: 1.4, viscosity at 23 ° C, D ca. 40 s "1 950 ⁇ 550 mPa-s, according to DIN EN ISO 3219 / A.3, OH-content, solid resin (calculated) about 3,3% Bayer MaterialScience AG.
- the catalyst lithium molybdate (c) was obtained as a coarsely crystalline salt from Aldrich and used according to the invention preparation of the nanoparticulate form in the stated amount of butyl acetate in the inventive example. It is contained in the amount of butyl acetate in the example according to the invention. Based on the solids content of the paint system, the amount of lithium molybdate was 250 ppm in the example according to the invention.
- the samples were allowed to flash at room temperature for a period of 10 minutes and then cross-linked at a temperature of 60 ° C. over a period of 30 minutes.
- the catalyst leads to a significantly accelerated drying, the z.T. 2 to 3 times faster than without catalyst. Thus, the effect of the catalyst is proved.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
La présente invention concerne de nouvelles nanoparticules de molybdate, leur procédé de fabrication par recristallisation, ainsi que leur utilisation.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006005165A DE102006005165A1 (de) | 2006-02-04 | 2006-02-04 | Verfahren zur Herstellung von Lithium-Molybdat-Nanopartikeln |
PCT/EP2007/000447 WO2007087988A1 (fr) | 2006-02-04 | 2007-01-19 | Procede de fabrication de nanoparticules de molybdate de lithium |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1984302A1 true EP1984302A1 (fr) | 2008-10-29 |
Family
ID=37807836
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07702880A Withdrawn EP1984302A1 (fr) | 2006-02-04 | 2007-01-19 | Procede de fabrication de nanoparticules de molybdate de lithium |
Country Status (5)
Country | Link |
---|---|
US (1) | US7732498B2 (fr) |
EP (1) | EP1984302A1 (fr) |
JP (1) | JP2009525245A (fr) |
DE (1) | DE102006005165A1 (fr) |
WO (1) | WO2007087988A1 (fr) |
Families Citing this family (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20100196246A1 (en) * | 2007-10-09 | 2010-08-05 | Headwaters Technology Innovation, Llc | Methods for mitigating agglomeration of carbon nanospheres using a crystallizing dispersant |
EP2154206A1 (fr) * | 2008-07-26 | 2010-02-17 | Bayer MaterialScience AG | Dispersions de nanoparticules stabilisées |
CN101665269B (zh) * | 2009-08-31 | 2011-04-13 | 广西民族大学 | 一种粒径可控的钼酸镉八面体的制备方法 |
CN102806357A (zh) * | 2011-06-02 | 2012-12-05 | 中国科学院过程工程研究所 | 一种高稳定性纳米金颗粒的制备方法 |
JP5786494B2 (ja) * | 2011-06-29 | 2015-09-30 | 日立化成株式会社 | モリブデン酸亜鉛微粒子含有スラリー組成物 |
JP5406962B2 (ja) * | 2012-06-14 | 2014-02-05 | 花王株式会社 | ナノ粒子の製造方法 |
PL3728381T3 (pl) | 2017-12-21 | 2022-05-02 | Covestro Deutschland Ag | Kleje mrozoodporne na bazie poliizocyjanianów |
WO2023187113A1 (fr) * | 2022-04-01 | 2023-10-05 | Covestro Deutschland Ag | Composition de revêtement à deux composants |
EP4279519A1 (fr) * | 2022-05-19 | 2023-11-22 | Covestro Deutschland AG | Composition de revêtement à deux composants |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2133314B (en) * | 1982-12-28 | 1986-02-26 | Dainippon Toryo Kk | Process for forming a corrosion resistant coating |
US4708753A (en) * | 1985-12-06 | 1987-11-24 | The Lubrizol Corporation | Water-in-oil emulsions |
FR2608942B1 (fr) * | 1986-12-31 | 1991-01-11 | Centre Nat Rech Scient | Procede de preparation de systemes colloidaux dispersibles d'une substance, sous forme de nanocapsules |
DE10145266A1 (de) * | 2001-09-14 | 2003-04-24 | Basf Coatings Ag | Polyurethane und Pfropfmischpolymerisate auf Polyurethanbasis sowie ihre Verwendung zur Herstellung von Beschichtungsstoffen, Klebstoffen und Dichtungsmassen |
US6720008B2 (en) * | 2002-01-22 | 2004-04-13 | Pr Pharmaceuticals, Inc. | Composition and method for the encapsulation of water-soluble molecules into nanoparticles |
DE10308106A1 (de) * | 2003-02-26 | 2004-09-09 | Bayer Aktiengesellschaft | Neue 2K-PUR-Systeme |
DE10308104A1 (de) * | 2003-02-26 | 2004-09-09 | Bayer Ag | Polyurethan-Beschichtungssysteme |
-
2006
- 2006-02-04 DE DE102006005165A patent/DE102006005165A1/de not_active Withdrawn
-
2007
- 2007-01-19 EP EP07702880A patent/EP1984302A1/fr not_active Withdrawn
- 2007-01-19 JP JP2008552713A patent/JP2009525245A/ja active Pending
- 2007-01-19 WO PCT/EP2007/000447 patent/WO2007087988A1/fr active Application Filing
- 2007-02-01 US US11/701,007 patent/US7732498B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
Title |
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See references of WO2007087988A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE102006005165A1 (de) | 2007-08-09 |
US20080004356A1 (en) | 2008-01-03 |
WO2007087988A1 (fr) | 2007-08-09 |
US7732498B2 (en) | 2010-06-08 |
JP2009525245A (ja) | 2009-07-09 |
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