WO2005070979A1 - Utilisation de copolymeres statistiques - Google Patents

Utilisation de copolymeres statistiques Download PDF

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Publication number
WO2005070979A1
WO2005070979A1 PCT/EP2004/014389 EP2004014389W WO2005070979A1 WO 2005070979 A1 WO2005070979 A1 WO 2005070979A1 EP 2004014389 W EP2004014389 W EP 2004014389W WO 2005070979 A1 WO2005070979 A1 WO 2005070979A1
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Prior art keywords
range
precursors
reacted
nanoparticles
emulsion
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PCT/EP2004/014389
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German (de)
English (en)
Inventor
Matthias Koch
Victor Khrenov
Markus Klapper
Klaus Muellen
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Merck Patent Gmbh
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Priority claimed from DE102004004209A external-priority patent/DE102004004209A1/de
Application filed by Merck Patent Gmbh filed Critical Merck Patent Gmbh
Priority to JP2006549912A priority Critical patent/JP2007519786A/ja
Priority to CA002554335A priority patent/CA2554335A1/fr
Priority to US10/587,304 priority patent/US20070282075A1/en
Priority to EP04803997A priority patent/EP1709092A1/fr
Publication of WO2005070979A1 publication Critical patent/WO2005070979A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/04—Making microcapsules or microballoons by physical processes, e.g. drying, spraying
    • B01J13/046—Making microcapsules or microballoons by physical processes, e.g. drying, spraying combined with gelification or coagulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/003—Organic compounds containing only carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/007—Organic compounds containing halogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/14—Derivatives of phosphoric acid
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/18—Quaternary ammonium compounds
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent

Definitions

  • the invention relates to the use of statistical copolymers as emulsifiers, in particular in the synthesis of nanoparticles, and to production processes for such particles.
  • inorganic nanoparticles inorganic nanoparticles in a polymer matrix can not only the mechanical properties such. B. impact strength, affect the matrix, but also changes their optical properties, such as wavelength-dependent transmission, color (absorption spectrum) and refractive index. Particle size plays an important role in mixtures for optical applications because the addition of a substance with a refractive index that differs from the refractive index of the matrix inevitably leads to light scattering and ultimately to opacity.
  • the decrease in the intensity of radiation of a defined wavelength when passing through a mixture shows a strong dependence on the diameter of the inorganic particles.
  • nanomaterials for dispersion in polymers requires not only the control of the particle size, but also the surface properties of the particles.
  • a simple mixing (eg by extrusion) of hydrophilic particles with a hydrophobic polymer matrix leads to an uneven distribution of the particles throughout the polymer and also to their aggregation.
  • their surface must therefore be at least hydrophobically modified.
  • the nanoparticulate materials in particular show a great tendency to form agglomerates, which remain even after a subsequent surface treatment.
  • nanoparticles can be precipitated directly from emulsions with a suitable surface modification almost without agglomerates if certain statistical copolymers are used as emulsifiers.
  • a first subject of the present invention is therefore the use of statistical copolymers containing at least one structural unit with hydrophobic residues and at least one structural unit with hydrophilic residues as an emulsifier, in particular in the synthesis of nanoparticles from emulsions.
  • Another object of the present invention is a method for producing polymer-modified nanoparticles, which is characterized in that in step a) an inverse emulsion containing one or more water-soluble precursors for the nanoparticles or a melt, with the aid of a statistical copolymer of at least one Monomer with hydrophobic residues and at least one monomer with hydrophilic residues is produced and particles are generated in a step b).
  • the syntheses of the inorganic materials often require high salt concentrations of precursor materials in the emulsion, the concentration additionally fluctuating during the reaction.
  • Low molecular weight surfactants react to such high salt concentrations that the stability of the emulsions is at risk (Paul Kent and Brian R. Saunders; Journal of Colloid and Interface Science 242, 437-442 (2001)).
  • the control of the Particle sizes are only possible to a limited extent (M.-H. Lee, CY Tai, CH Lu, Korean J. Chem. Eng. 16, 1999, 818-822).
  • K. Landfester (Adv. Mater. 2001, 13, No. 10, 765- 768) suggests the use of high molecular weight surfactants (PEO-PS block copolymers) in combination with ultrasound to produce nanoparticles in the particle size range from about 150 to about 300 nm from metal salts.
  • PEO-PS block copolymers high molecular weight surfactants
  • the statistical copolymers to be preferably used according to the invention show a weight ratio of structural units with hydrophobic radicals to structural units with hydrophilic radicals in the statistical copolymers in the range 1: 2 to 500: 1, preferably in the range 1: 1 to 100: 1 and particularly preferably in the range 7: 3 to 10: 1.
  • X and Y correspond to the residues of conventional nonionic or ionic monomers and R 1 stands for hydrogen or a hydrophobic side group, preferably selected from the branched or unbranched alkyl residues with at least 4 carbon atoms in which one or more, preferably all, H atoms are replaced by fluorine atoms , and R 2 stands for a hydrophilic side group, which preferably has a phosphonate, sulfonate, polyol or polyether radical, and wherein within one molecule -XR 1 and -YR 2 can each have several different meanings, the inventive Meet requirements in a special way.
  • R 1 stands for hydrogen or a hydrophobic side group, preferably selected from the branched or unbranched alkyl residues with at least 4 carbon atoms in which one or more, preferably all, H atoms are replaced by fluorine atoms
  • R 2 stands for a hydrophilic side group, which preferably has a phosphonate, sulf
  • R 2 preferably represents a side group - (CH2) m - (N + (CH 3 ) 2) - (CH2) n-S0 3 - or a side group - (CH 2 ) m- (N + (CH 3 ) 2 ) - (CH 2 ) n-P0 3 2 " , where m stands for an integer from the range from 1 to 30, preferably from the range 1 to 6, particularly preferably 2, and n stands for an integer from the range from 1 to 30, preferably from the range 1 to 8, in particular preferably 3, use advantageously.
  • LMA lauryl methacrylate
  • DMAEMA dimethylaminoethyl methacrylate
  • copolymers may contain styrene, vinylpyridone, vinylpyridine, halogenated styrene or methoxystyrene, these examples being no limitation.
  • polymers are used which are characterized in that at least one structural unit is an oligomer or polymer, preferably a macromonomer, polyether, Polyolefins and polyacrylates are particularly preferred as macromonomers.
  • Water-soluble metal compounds preferably silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and / or zirconium compounds, can be used as precursors for the inorganic nanoparticles
  • Precursors preferably for the production of corresponding metal oxide particles, are preferably reacted with an acid or alkali.
  • Mixed oxides can be obtained in a simple manner by suitable mixing of the corresponding precursors.
  • suitable precursors is not difficult for the person skilled in the art; all compounds are suitable which are suitable for precipitating the corresponding target compounds from aqueous solution.
  • An overview of suitable precursors for the production of oxides is, for example, in Table 6 in K.
  • Osseo-Asare “Microemulsion-mediated Synthesis of nanosize Oxide Materials” in: Kumar P., Mittal KL, (editors), Handbook of microemulsion science and technology, New York: Marcel Dekker, Inc., pp. 559-573, the content of which expressly belongs to the disclosure content of the present application.
  • Hydrophilic melts can also serve as precursors for nanoparticles in the sense of this invention. In this case, a chemical conversion to produce the nanoparticles is not absolutely necessary.
  • alkali metal or alkaline earth metal silicates preferably sodium silicates
  • at least one soluble compound of a noble metal preferably silver nitrate, is converted to the metal with a reducing agent, preferably citric acid.
  • a soluble metal compound preferably a soluble Pb, Cd, Zn compound, is reacted with hydrogen sulfide to give the metal sulfide.
  • a soluble metal compound such as preferably e.g. B. calcium chloride, implemented with carbon dioxide to a nanoparticulate metal carbonate.
  • Nanoparticles which are particularly preferably produced are those which essentially consist of oxides or hydroxides of silicon, cerium, cobalt, chromium, nickel, zinc, titanium, iron, yttrium and / or zirconium.
  • the particles preferably have an average particle size determined by means of dynamic light scattering or
  • the distribution of particle sizes is narrow, i.e. the fluctuation range is less than 100% of the mean, particularly preferably a maximum of 50% of the mean.
  • the nanoparticles are a Have absorption maximum in the range 300-500 nm, preferably in the range up to 400 nm, particularly preferred nanoparticles absorbing radiation, particularly in the UV-A range.
  • the emulsion process can be carried out in various ways:
  • particles are usually produced in step b) by reacting the precursors or by cooling the melt.
  • the precursors can be reacted with an acid, an alkali, a reducing agent or an oxidizing agent.
  • the droplet size in the emulsion is in the range from 5 to 500 nm, preferably in the range from 10 to 200 nm.
  • the droplet size in the given system is adjusted in the manner known to the person skilled in the art, the oil phase being individually matched to the reaction system by the person skilled in the art.
  • ZnO particles for example, toluene and cyclohexane have proven to be an oil phase.
  • co-emulsifier preferably a non-ionic surfactant
  • Preferred co-emulsifiers are optionally ethoxylated or propoxylated, longer-chain alkanols or alkylphenols with different degrees of ethoxylation or propoxylation (e.g. adducts with 0 to 50 mol of alkylene oxide).
  • Dispersing aids can also be used advantageously, preferably water-soluble high-molecular organic Compounds with polar groups, such as polyvinyl pyrrolidone, copolymers of vinyl propionate or acetate and vinyl pyrrolidone, partially saponified copolymer list of an acrylic ester and acrylonitrile, polyvinyl alcohols with different residual acetate content, cellulose ethers, gelatin, block copolymers, modified starch, low molecular weight, carbon and / or sulfonic acid groups or mixtures of these substances can be used.
  • polar groups such as polyvinyl pyrrolidone, copolymers of vinyl propionate or acetate and vinyl pyrrolidone, partially saponified copolymer list of an acrylic ester and acrylonitrile, polyvinyl alcohols with different residual acetate content, cellulose ethers, gelatin, block copolymers, modified starch, low molecular weight, carbon and / or
  • Particularly preferred protective colloids are polyvinyl alcohols with a residual acetate content of less than 40, in particular 5 to 39 mol% and / or vinylpyrrolidone-aminopropionate copolymers with a vinyl ester content of less than 35, in particular 5 to 30% by weight.
  • reaction conditions such as temperature, pressure and reaction time
  • desired combinations of properties of the required nanoparticles can be set.
  • a second emulsion in which a reaction partner for the precursors is emulsified is mixed with the precursor emulsion from step a) in step b).
  • This 2-emulsion process allows the production of particles with a particularly narrow particle size distribution. It can be particularly advantageous if the two emulsions are mixed together by the action of ultrasound.
  • a precipitant is added to the precursor emulsion in step b) which is soluble in the continuous phase of the emulsion.
  • the precipitation then takes place by diffusing the precipitant into the Micelles containing precursor.
  • titanium dioxide particles can be obtained in this way by diffusing pyridine in micelles containing titanyl chloride or silver particles by diffusing long-chain aldehydes in micelles containing silver nitrate.
  • the nanoparticles according to the invention are used in particular in polymers.
  • Polymers into which the nanoparticles according to the invention can be readily incorporated are in particular polycarbonate (PC), polyethylene terephthalate (PETP), polyimide (PI), polystyrene (PS), polymethyl methacrylate (PMMA) or copolymers which contain at least a proportion of one of the polymers mentioned.
  • Incorporation can be carried out by customary methods for the production of polymer preparations. For example, that
  • Polymer material with nanoparticles according to the invention preferably in an extruder or kneader, are mixed.
  • kneaders can also be used.
  • the polymers can also be dispersions of
  • the polymer preparations according to the invention containing the nanoparticles are also particularly suitable for coating surfaces. So that the surface or that under the Protect coating material, for example, from UV radiation.
  • the first step involves the synthesis of a statistical copolymer of dodecyl methacrylate (lauryl methacrylate; LMA) and dimethylaminoethyl methacrylate (DMAEMA). Control of the molecular weight can be achieved by adding mercaptoethanol. The copolymer thus obtained is modified with 1,3-propane sultones to add saturated groups.
  • LMA dodecyl methacrylate
  • DMAEMA dimethylaminoethyl methacrylate
  • LMA and DMAEMA in an amount corresponding to Table 1 below, are initially introduced into 12 g of toluene and polymerized under free radicals under argon at 70 ° C. after the start of the reaction by adding 0.033 g of AIBN in 1 ml of toluene.
  • the chain growth can be controlled by adding 2-mercaptoethanol (see Table 1).
  • the crude polymer is washed, freeze-dried and then with 1,3-propanesultone, as in V. Butun, CE Bennett, M. Vamvakaki, AB Löwe, NC Billingham, SP Armes, J. Mater. Chem., 1997, 7 (9), 1693-1695.
  • ZnO particles are precipitated using the following method: 1. Preparation of an inverse emulsion of an aqueous solution of 0.4 g of Zn (AcO) 2 * 2H 2 0 in 1, 1 g of water (emulsion 1) and 0.15 g of NaOH in 1 , 35g water (emulsion 2) using ultrasound. Emulsion 1 and Emulsion 2 each contain 150 mg of a random copolymer E1 - E5 from Table 1. 2. Ultrasound treatment of the mixture of Emulsion 1 and Emulsion 2 and subsequent drying. 3. Purification of sodium acetate by washing the solid obtained with water. 4. Drying and redispersion of the powder functionalized by the emulsifier on the surface by stirring in toluene.
  • example 2 leads to a product consisting of the synthesized macro surfactant and zinc oxide particles.
  • Example 2 with the commercially available emulsifier, ABIL EM 90 ® (Cetyl Dimethicone copolyol, Fa. Goldschmidt) instead of the random copolymer of Example 1 does not lead to a stable emulsion.
  • the particles obtained have diameters between 500 and 4000 nm.
  • the precipitation of Si0 2 particles is carried out according to the following method: I. Production of an inverse emulsion of an aqueous solution of Na2Si0 3 (emulsion 1) and H 2 S0 4 (emulsion 2) by means of ultrasound (concentrations according to Table 2). 2. Ultrasound treatment of the mixture of emulsion 1 and emulsion 2 and subsequent drying. 3. Purification by washing the solid obtained with water. 4. Drying and redispersion of the powder obtained. FT-IR spectroscopy and X-ray diffraction demonstrate the formation of SiO 2 and the absence / absence of sodium silicate. Thus, the step leads to a product consisting of the synthesized macro surfactant and silica particles.
  • a dispersion of the particles from Example 2-E1 in PMMA lacquer is produced by mixing, applied to glass substrates and dried.
  • the ZnO content after drying is 10% by weight.
  • the films show a barely perceptible cloudiness. Measurements with a UV-VIS spectrometer confirm this impression. Depending on the layer thickness, the sample shows the following absorption values (the percentage of the incident light that is lost in transmission is indicated)

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Abstract

Utilisation de copolymères statistiques contenant au moins une unité structurale ayant des restes hydrophobes et au moins une unité structurale ayant des restes hydrophiles en tant qu'émulsifiants, en particulier pour la synthèse de nanoparticules. La présente invention concerne également un procédé de production desdites particules selon lequel, dans l'étape (a), une émulsion inverse contenant un ou plusieurs précurseurs hydrosolubles des nanoparticules ou une masse fondue est préparée à l'aide d'un copolymère statistique produit à partir d'au moins un monomère ayant des restes hydrophobes et d'au moins un monomère ayant des restes hydrophiles, et dans l'étape (b), des particules sont produites.
PCT/EP2004/014389 2004-01-27 2004-12-17 Utilisation de copolymeres statistiques WO2005070979A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2006549912A JP2007519786A (ja) 2004-01-27 2004-12-17 統計的共重合体の利用
CA002554335A CA2554335A1 (fr) 2004-01-27 2004-12-17 Utilisation de copolymeres statistiques
US10/587,304 US20070282075A1 (en) 2004-01-27 2004-12-17 Use Of Statistical Copolymers
EP04803997A EP1709092A1 (fr) 2004-01-27 2004-12-17 Utilisation de copolymeres statistiques

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE102004004209A DE102004004209A1 (de) 2004-01-27 2004-01-27 Verwendung von statistischen Copolymeren
DE102004004209.8 2004-01-27
EP04023002 2004-09-28
EP04023002.1 2004-09-28

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JP (1) JP2007519786A (fr)
KR (1) KR20070004599A (fr)
CA (1) CA2554335A1 (fr)
TW (1) TW200540191A (fr)
WO (1) WO2005070979A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006114181A2 (fr) * 2005-04-25 2006-11-02 Merck Patent Gmbh Nanoparticules
WO2007059843A1 (fr) * 2005-11-25 2007-05-31 Merck Patent Gmbh Nanoparticules
FR2914647A1 (fr) * 2007-04-05 2008-10-10 Rhodia Recherches & Tech Copolymere comprenant des unites betainiques et des unites hydrophobes et/ou amphiphiles,procede de preparation,et utilisations.
DE102007032189A1 (de) 2007-06-22 2008-12-24 Merck Patent Gmbh Härtungskatalysator
DE102007029283A1 (de) 2007-06-22 2008-12-24 Merck Patent Gmbh Härtungsbeschleuniger
DE102010018073A1 (de) 2010-04-20 2011-10-20 Aesculap Ag Copolymermodifizierte Nanopartikel, insbesondere zur Verwendung bei medizintechnischen Gegenständen
WO2012052148A1 (fr) 2010-10-19 2012-04-26 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Procédé de préparation ultrarapide de nanoparticules polymères
WO2012052147A1 (fr) 2010-10-19 2012-04-26 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Procédé de modification de polymères, en particulier, de nanoparticules polymères
ITPA20110012A1 (it) * 2011-08-30 2013-03-01 Salvo Santina Di Processo innovativo sonochimico che impiega cavitazione ultrasonica per la sintesi di nanoparticelle amorfe monodisperse di biossido di silicio e metodo per preparare un composto di litio silicato idrosolubile ad alta performance, da applicare in sit
US9399075B2 (en) 2008-12-29 2016-07-26 General Electric Company Nanoparticle contrast agents for diagnostic imaging
WO2019092036A1 (fr) 2017-11-07 2019-05-16 Clariant Plastics & Coatings Ltd Agent dispersant pour pigments dans des préparations de colorants non aqueuses

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1830652B1 (fr) 2004-12-30 2013-11-06 Rhodia Chimie Composition herbicide comprenant un aminophosphate ou un sel d'aminophosphate, un betaine et un oxyde d'amine
CA2629862C (fr) 2005-11-14 2014-03-18 Rhodia Inc. Compositions d'adjuvant agricole, compositions de pesticides et procedes d'utilisation de telles compositions
US20100029483A1 (en) 2006-10-16 2010-02-04 Rhodia Inc. Agricultural adjuvant compositions, pesticide compositions, and methods for using such compositions
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WO2008125512A1 (fr) * 2007-04-05 2008-10-23 Rhodia Operations Copolymère comprenant des unités bétaïniques et des unités hydrophobes et/ou amphiphiles, procédé de préparation et utilisations.
DE102007032189A1 (de) 2007-06-22 2008-12-24 Merck Patent Gmbh Härtungskatalysator
DE102007029283A1 (de) 2007-06-22 2008-12-24 Merck Patent Gmbh Härtungsbeschleuniger
US9399075B2 (en) 2008-12-29 2016-07-26 General Electric Company Nanoparticle contrast agents for diagnostic imaging
WO2011131681A1 (fr) 2010-04-20 2011-10-27 Laser Zentrum Hannover E.V. Nanoparticules modifiées par un copolymère, en particulier pour une utilisation dans des articles médicaux
US9243089B2 (en) 2010-04-20 2016-01-26 Stephan Barcikowski Copolymer-modified nanoparticles, especially for use in medical articles
DE102010018073A1 (de) 2010-04-20 2011-10-20 Aesculap Ag Copolymermodifizierte Nanopartikel, insbesondere zur Verwendung bei medizintechnischen Gegenständen
WO2012052148A1 (fr) 2010-10-19 2012-04-26 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Procédé de préparation ultrarapide de nanoparticules polymères
WO2012052147A1 (fr) 2010-10-19 2012-04-26 MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. Procédé de modification de polymères, en particulier, de nanoparticules polymères
US8921442B2 (en) 2010-10-19 2014-12-30 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E. V. Ultra fast process for the preparation of polymer nanoparticles
US8921444B2 (en) 2010-10-19 2014-12-30 Max-Planck-Gesellschaft Zur Foerderung Der Wissenschaften E.V. Process for the modification of polymers, in particular polymer nanoparticles
ITPA20110012A1 (it) * 2011-08-30 2013-03-01 Salvo Santina Di Processo innovativo sonochimico che impiega cavitazione ultrasonica per la sintesi di nanoparticelle amorfe monodisperse di biossido di silicio e metodo per preparare un composto di litio silicato idrosolubile ad alta performance, da applicare in sit
WO2019092036A1 (fr) 2017-11-07 2019-05-16 Clariant Plastics & Coatings Ltd Agent dispersant pour pigments dans des préparations de colorants non aqueuses

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CA2554335A1 (fr) 2005-08-04

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