EP2102271A1 - Procédé de production de dispersions - Google Patents

Procédé de production de dispersions

Info

Publication number
EP2102271A1
EP2102271A1 EP07819836A EP07819836A EP2102271A1 EP 2102271 A1 EP2102271 A1 EP 2102271A1 EP 07819836 A EP07819836 A EP 07819836A EP 07819836 A EP07819836 A EP 07819836A EP 2102271 A1 EP2102271 A1 EP 2102271A1
Authority
EP
European Patent Office
Prior art keywords
oligomer
aqueous dispersion
polymer
inorganic particles
water
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Withdrawn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
EP07819836A
Other languages
German (de)
English (en)
Inventor
Gerhard Jonschker
Matthias Koch
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Merck Patent GmbH
Original Assignee
Merck Patent GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Merck Patent GmbH filed Critical Merck Patent GmbH
Publication of EP2102271A1 publication Critical patent/EP2102271A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6659—Compounds of group C08G18/42 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
    • C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
    • C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/10—Treatment with macromolecular organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/12—Treatment with organosilicon compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/62—L* (lightness axis)
    • 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
    • C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
    • C01P2006/64—Optical properties, e.g. expressed in CIELAB-values b* (yellow-blue axis)
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2190/00—Compositions for sealing or packing joints
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • 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
    • C08K9/02—Ingredients treated with inorganic substances

Definitions

  • the present invention relates to a process for preparing an aqueous dispersion comprising at least one polymer and / or oligomer and inorganic surface-modified particles, wherein the
  • WO 2006/008120 discloses aqueous binder dispersions containing nanoparticles which contain nanoscale polymer particles dispersed in water or an aqueous colloidal solution, which envelop the nanoparticles.
  • the particles mentioned are produced by shearing the nanoparticles into an anhydrous polymer phase and incorporating the nanoparticle-containing polymer particles under shear in water.
  • the said production method has the disadvantage that high shear forces act on the nanoparticles and the polymer particles, which can lead to a detachment of the polymer shell from the nanoparticles.
  • the two-step process is very complex.
  • only nanoparticles in the form of dry powders or anhydrous dispersions are suitable for incorporation into the anhydrous polymer phase.
  • powdery nanoparticles are highly agglomerated and under normal conditions (shear forces) no longer completely deagglomerable. This applies in particular to pyrogenic silicas, as used in WO 2006/008120.
  • the preparation of anhydrous nanoparticle dispersions is very complicated and therefore expensive.
  • the nanoparticles must be compatibilized with the polymer and solvent phase. By introducing reactive nanoparticles into a solvent phase, the
  • the dispersion obtained should be applicable in the coating and coating technology as well as in adhesive applications by conventional methods such as rolling, spraying, brushing, casting or rolling.
  • This object is achieved by a process for producing an aqueous dispersion comprising at least one polymer and / or oligomer (B) and inorganic surface-modified particles, wherein the polymer and / or oligomer (B) envelopes the modified surface inorganic particles, and by the process dissolved dispersions dissolved.
  • the process for producing the dispersion according to the invention comprises the following steps: a) preparing a dispersion of inorganic particles in water or a water-solvent mixture and modifying the surface of the inorganic particles in the aqueous dispersion by adding a surface modifier b) preparing an oligomer (A) Polymerization of suitable monomers in a solvent or solvent mixture c) mixing the oligomer (A) from step b) with the aqueous dispersion from step a) and further polymerizing the oligomer (A) to obtain a polymer and / or oligomer (B).
  • step a) of the method according to the invention is first a
  • the dispersion may be prepared by dispersing inorganic particles in water or a water-solvent mixture.
  • the dispersion is preferably carried out by stirring.
  • Suitable solvents in the water-solvent mixture are, for example, alcohols, ketones or cyclic ethers, in particular ethanol, acetone, ethyl methyl ketone, THF or dioxane.
  • the proportion of the solvent in the water / solvent mixture can be up to 95% by weight, preferably up to 80% by weight, based on the mixture.
  • the dispersion can be carried out at temperatures between freezing and boiling point of the particular solvent used, preferably at room temperature.
  • the inorganic particles are prepared from suitable precursors directly in water or in the water-solvent mixture generated.
  • suitable precursors are reacted in water or a water-solvent mixture to form corresponding particles which are then dispersed in water or in the water / solvent mixture.
  • Corresponding processes are known to the person skilled in the art and are described, for example, in US Pat. No. 4,775,520 (Unger et al., Stöber Synthesis) or Her "The Chemistry of Silica” or Brinker / Scherer "The Sol-GeI Process". - A -
  • Suitable particles for the present invention are preferably selected from the group of oxides, mixed oxides, carbides, borides and nitrides of elements of II. To IV. Main group and / or elements of the I. to VIII. Subgroup of the Periodic Table including the lanthanides.
  • the inorganic particles are in particular preferably nanoparticles, in particular selected from the group consisting of hydrophilic and hydrophobic, in particular hydrophilic, nanoparticles based on oxides or hydroxides of silicon, titanium, zinc, aluminum, cerium, cobalt, chromium, nickel, Iron, yttrium and / or zirconium, or with oxides or hydroxides of silicon coated metals, such as Ag, Cu, Fe, Au, Pd, Pt or alloys.
  • the particles based on oxides or hydroxides of titanium, zinc, aluminum, cerium, cobalt, chromium, nickel, iron, yttrium and / or zirconium may optionally be coated with oxides or hydroxides of silicon.
  • the individual oxides can also be present as mixtures.
  • the inorganic particles preferably have an average particle size, determined by means of a Malvern ZETASIZER (dynamic light scattering) or transmission electron microscope, of from 3 to 200 nm, in particular from 5 to 80 nm and very particularly preferably from 10 to 50 nm. Particular preference is given to using nanoparticles, particularly preferably based on silicon dioxide, aluminum oxide, cerium oxide, zirconium oxide and / or titanium dioxide.
  • nanoparticles in the form of powders are silicon dioxides, eg. As pyrogenic silicic acids such as Aerosil 200, Aerosil TT 600, Aerosil OX 50 and Aerosil 7200 from. Degussa AG or nanoscale silica produced by plasma processes, such as. KADESIT040-100 from KDS NANO, titanium dioxides such as pyrogenic titanium dioxide P25 from Degussa AG, or Hombitec RM 300 from Sachtleben Chemie GmbH, aluminum oxides, eg. As pyrogenic alumina C from the company. Degussa AG or z. B.
  • NanoTek TM alumina produced by plasma processes PureNano TM alumina from NanoProducts Co ⁇ oration or NanoDur TM alumina from Nanophase Technologies Corporation, as well as other nanoscale metal oxides that have been prepared by means of physical-chemical processes, such as. As flame pyrolysis or plasma processes are prepared, for. As cerium oxides such as NanoTek
  • nanohektorites which are sold, for example, by the company S ⁇ dchemie under the brand Optigel® or by the company Laporte under the brand Laponite®, can also be used.
  • silica sols (SiO 2 in water) prepared from ion-exchanged waterglass are also particularly preferred.
  • the surface of the inorganic particles in the aqueous dispersion is modified by the addition of a surface modifier.
  • Modification of the surface in the sense of the present invention means that compounds are present under the covalent bond or bound by means of adsorptive interactions on the surface of the inorganic particles.
  • the modification of the surface of the inorganic particles preferably takes place by covalent bonding of corresponding compounds on the surface. In this way, a particularly stable system of particles and surface modifier is produced.
  • Suitable surface modifiers are in the broadest sense compounds of the general formula (I) [(S-) o L-] m M (R) n (H) p (I) wherein the indices and the variables have the following meaning:
  • L is at least divalent organic linking group; H hydrolyzable monovalent group or hydrolyzable atom;
  • M is a two to six valent main group and subgroup metal
  • R is a monovalent organic radical; o is an integer from 1 to 5; m + n + p is an integer from 2 to 6; p is an integer from 1 to 6; m and n are zero or an integer from 1 to 5.
  • the group S may for example be selected from the group of the amino, amide, carboxy, mercapto, isocyanato, hydroxy, alkoxy, alkoxycarbonyl, acryloyloxy, methacryloxy or epoxy groups.
  • Group L are usually alkyl, alkenyl, aryl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl radicals, preferably each having 1 to 12 and especially 1 to 8 carbon atoms, including cyclic forms.
  • the group H can be any group which hydrolyzes under basic or acidic conditions, for example from the class of alkoxy groups.
  • M is preferably Ti, Zr, Si or Al. For example, it may be isopropyl triisostearoyl titanate or
  • Neopentyl (diallyl) oxytrineodecanoylzirconate used as a surface modifier.
  • M Si
  • R is very particularly preferably selected from alkoxy groups.
  • Alkoxysilanes which are particularly preferred for the purposes of the present invention correspond to the general formula (II): RVxSi (OR) x (II) in which the radicals R are identical or different from one another, are preferably identical and represent optionally substituted, preferably unsubstituted hydrocarbon groups having 1 to 8, preferably 1 to 6 and particularly preferably 1 to 4 carbon atoms.
  • R is methyl or ethyl.
  • the radicals R 1 may be identical or different from each other, each represents an optionally substituted hydrocarbon group having 1 to 20 carbon atoms, x in formula (II) is 1, 2 or 3.
  • radicals R 1 are alkyl, alkenyl, aryl, alkylaryl, arylalkyl, arylalkenyl, alkenylaryl radicals, preferably having in each case 1 to 12 and in particular 1 to 8 carbon atoms, cyclic forms being included ,
  • the radicals R 1 carry one or more substituents from the group of halogens and optionally substituted amino, amide, carboxy, mercapto, isocyanato, hydroxy, alkoxy, alkoxycarbonyl, acryloyloxy, methacryloxy or epoxy groups ,
  • Particularly preferred among the above alkoxysilanes of the general formula (II) is at least one in which at least one radical R 1 has a grouping which can undergo a polyaddition, polymerization or a polycondensation reaction.
  • Polyaddition or polycondensation reaction capable grouping is preferably an amino, diamino, polyamino, hydrazino, ketimino, hydroxy or epoxy group.
  • preferred organically modified alkoxysilanes of the general formula (II) for use as surface modifier in the present invention are those in which x is 2 or 3 and in particular 3 and one radical R 1 or the only radical R 1 for ⁇ -glycidyloxy C 2 - 6 alkyl.
  • the surface modifiers mentioned are reactive compounds that can react with the binder and / or binder precursors.
  • the radical R ' has an amino, diamino, polyamino, hydrazino or ketimino group. Be as
  • the said surface modifiers can react via the amino, diamino, polyamino, hydrazino or Ketimino phenomenon with the polymer and / or oligomer and in this way a particularly strong linkage of particles and polymer guarantee.
  • the rapid reaction between an amino group and a terminal isocyanate group preferably present in the oligomer (A) ensures that the growth process on the particles is faster than the reaction between the isocyanate group and water.
  • the particles can thus serve as growth centers for the polymers and are therefore structurally determining. This raises the possibility of particle size control of the polymer / nanoparticle dispersion. Furthermore, crosslinking of the polymer chains with each other is reduced, which lowers the viscosity of the entire system.
  • silanes are 3-glycidoxypropyltri (m) ethoxysilane, 3,4-epoxybutyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • Particularly suitable compounds are 3-aminopropyltriethoxysilane, N-ethyl-gamma-aminoisobutyltriethoxysilane, secondary aminosilanes (A-Link 15, Y9669, bis-gamma-triethoxysilylpropylamine, from GE Silicones) or N-butylaminopropyltrimethoxysilane, where 3-aminopropyltriethoxysilane and N-butylaminopropyltrimethoxysilane very particularly preferably be used as a surface modifier.
  • step b) of the process according to the invention an oligomer (A) by polymerization of suitable monomers in a solvent or
  • the oligomer (A) preferably has terminal isocyanate groups, epoxy groups and optionally radically polymerizable groups. Furthermore, the oligomer (A) obtained in step b) may contain radiation-curable groups. For this purpose, UV / VIS, ⁇ , ⁇ electron beams or other high-energy rays come into question. However, it is also possible that the aqueous dispersion is a non-radiation-curing, e.g. air-forced, forced or under Einbrennclaim contains drying polymer and / or oligomer, which can be used both in one-component and in multicomponent coating compositions and optionally
  • the oligomer (A) particularly preferably also has ionic groups, precursors of ionic groups, for example carboxylic acids, and / or amphiphilic groups.
  • the oligomers (A) typically consist of polyethers, polyesters,
  • the added oligomer (A) is selected from the class of terminal isocyanate-modified polyurethanes / polyureas, for example as polyurethane prepolymers, as capped prepolymers or as reacted polyurethanes in the form of a melt or solution / dispersion.
  • polyisocyanates and polyols are suitable as precursors for the oligomer (A).
  • common precursors which are suitable for the preparation of corresponding polyurethane polymers include, for example, HDI (hexamethylene diisocyanate), IPDI (isophorone diisocyanate), diols, 2,2 ' -
  • silanes into the polyurethane prepolymer, for example aminosilanes or hydroxy-functional silanes.
  • a preferred embodiment consists in that the polyurethane prepolymer also has UV-curable groups, for example by copolymerizing HEMA or maleic / fumaric acid derivatives into the prepolymer.
  • the preparation of the polymers and / or oligomers (A) can be carried out catalytically or thermally induced. In the simplest embodiment, the preparation of the oligomers (A) takes place catalytically.
  • Suitable catalysts are, for example, organic tin compounds, such as dibutyltin dilaurate or metal salts of
  • Ethylhexanoic acid such as: zinc ethylhexanoate.
  • All methods known to the person skilled in the art for the preparation of polyesters, polyethers, polyurethanes, polyureas or mixtures / blends can be used in the step according to the invention.
  • the reaction time of the preparation of the oligomers (A) according to step b) of the process according to the invention is usually from a few minutes to several hours.
  • step c) of the process according to the invention the oligomer (A) from step b) and the aqueous dispersion from step a) are mixed and the polymer and / or oligomer (B) are prepared by further polymerization of the oligomer (A).
  • the oligomer (A) obtained in step b) and the dispersion obtained from step a) are mixed. This is done in the simplest case by simply stirring the corresponding oligomer (A), for example by the use of shear forces.
  • the amount of oligomer (A) is chosen so that in the aqueous dispersion, the proportion of the oligomer (A) is 5 to 70 wt .-%.
  • the oligomer (A) on to the polymer and / or oligomer (B) are reacted.
  • all polymerization methods known to the person skilled in the art are suitable; the preparation of the polymer and / or oligomer (B) is preferably carried out by a polyaddition, polycondensation or by anionic polymerization in solution.
  • the precursors already used in the preparation of the oligomers (A) can be used for the preparation of the corresponding polymers and / or oligomers (B).
  • aqueous dispersions comprising at least one polymer and / or oligomer (B) and inorganic surface-modified particles, wherein the polymer and / or oligomer (B) envelops the inorganic surface-modified particles obtainable by a process according to the present invention
  • the surface modifiers are covalently bonded to the surface of the particles.
  • the surface-modified inorganic particles can be more consistently incorporated into the polymer and / or oligomer (B) to be produced in the last step of the process according to the invention, because the
  • dispersions of the invention have the advantage that water-based nanoparticle dispersions can be used and can be dispensed with the difficult transfer of the particles in solvent-based dispersions. Furthermore, the nanoparticles act as
  • Nucleating agents and structuring agent for the growing polymers This makes it possible to control the particle size of the dispersions. Since no deagglomeration of the particles is necessary, the dispersion can be prepared under milder conditions (lower shear forces). The viscosity is lower by using non-agglomerated or unaggregated particles. Pre-crosslinking of polymers and particles in the solvent phase is avoided. Furthermore, the formation of polymer droplets is favored, containing only a nanoparticle as a core. Due to the covalent attachment and the "burying" of the inorganic nanoparticles under the polymer shell
  • the polymer and / or oligomer (B) in the dispersion according to the invention preferably has a molecular weight of at least 500 g / mol, more preferably of at least 800 g / mol to max. 500,000 g / mol on.
  • the molecular weight is preferably between 5,000 and 50,000 g / mol,
  • Polymer particles preferably have an average particle diameter between 20 and 500 nm, more preferably between 30 and 200 nm.
  • the nanoparticles contained in the polymer particles since they are enveloped by the polymer of the polymer particle, must have a smaller particle diameter than the polymer particles themselves.
  • the aqueous dispersion according to the present invention preferably contains 5 to 70% by weight, preferably 5 to 60% by weight, of nanoparticle-containing polymer particles based on the entire composition.
  • the aqueous dispersion contains
  • Suitable emulsifiers are saturated and unsaturated fatty alcohol ethoxylates having 8 to 15 C atoms in the fatty alkyl radical, alkylphenol ethoxylates having 6 to 13 C atoms in the alkyl radical and 4 to 100 ethylene oxide units, preferably lauryl alcohol ethoxylates, isotridekanol ethoxylates and octyl and nonylphenol ethoxylates having from 6 to 50 ethylene oxide units.
  • emulsifiers of a hydrophilic and a hydrophobic component in the ratio 1: 5 to 5: 1, e.g. one part lauryl alcohol 4 EO and three parts lauryl alcohol 40 EO.
  • the emulsifiers are used in a total amount of 0 to 15% by volume of the dispersion, preferably 0.8 to 10% by volume of the dispersion.
  • esters and ethoxylated esters of sorbitan such as those offered under the trademarks Tween and Span.
  • Tween 20 and Span 60 in the weight% ratio 1: 1 to 1: 7. More preferably, 3 to 15% by weight of the hydrophobic
  • Emulsifier replaced by oleylsarcoside.
  • the resulting dispersions are storage stable, without sedimentation and without changing the particle size distribution.
  • the protective colloids and / or emulsifiers are preferably used in an amount of 0.1 to 10 wt .-%, based on the total dispersion.
  • additives and additives in the aqueous dispersion preference is given to catalysts, co-catalysts, free-radical formers, photoinitiators, photosensitizers, water repellents, matting agents, lubricants, defoamers, deaerators, wetting agents, leveling agents, thixotropic agents, thickeners, inorganic and organic
  • additives and additives are water-soluble monomers which are polymerizable thermally and / or with high-energy radiation, preferably (meth) acrylic acid, (meth) acrylamide,
  • esters of meth (acrylic acid) with branched and / or linear C 1 -C 6 -alkyl radicals are used as additives / additives.
  • the aqueous dispersion preferably has a viscosity in the range of 1 to 800 mPas at 20 ° C.
  • aqueous dispersions according to the invention are used as coating and coating compositions or as adhesives and sealants. They are preferably used for the production of scratch, abrasion and adhesion-resistant layers, layers with increased chemical or mechanical strength and / or barrier layers.
  • Nanoparticle-containing varnish of the present invention has improved gloss retention (Example 2) and is thus more scratch resistant.
  • Coating and coating compositions or adhesives and sealants containing dispersions according to the present invention are likewise provided by the present invention.
  • the subject matter according to the application is intended to be explained in more detail with reference to the following examples, without restricting it to the specific embodiments mentioned here.
  • Example 1a Preparation of a PU Dispersion as Reference:
  • the entire mixture is further mixed for 20 minutes under high shear forces.
  • the resulting PU dispersion is filtered through a 280 ⁇ m fast sieve and has a pH of 8.5 and a solids content of 41.5%.
  • the dispersion is knife-coated with a 200 micron doctor blade on a black / white paint cards and at 80 0 C for 30 min. dried.
  • Example 1b Preparation of a Nanoparticle Dispersion
  • the mixture is rapidly 13.14 g of triethylamine and 126 g of a 20% dispersion of aminopropyltrimethoxysilane-modified SiO 2 nanoparticles (with 2% by mass of aminosilane, based on the dry mass) supplied in deionized water.
  • deionized water supplied in deionized water.
  • 18 g of 2-methylpentamethylenediamine and 382 g of deionized water are mixed and added slowly to the mixture with constant stirring.
  • the entire mixture is further mixed for 20 minutes under high shear forces.
  • the resulting PU dispersion is filtered through a 280 ⁇ m fast sieve and has a pH of 8.5 and a solids content of 41.5%.
  • the dispersion is knife-coated with a 200 micron doctor blade on a black / white paint cards and at 80 0 C for 30 min. dried.
  • the paints were after application and drying on the color cards with a commercial Glossmeter (Byk-Gardner) at 20 °

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

L'invention concerne un procédé permettant de produire une dispersion aqueuse comprenant au moins un polymère et/ou un oligomère, ainsi que des particules inorganiques à surface modifiée. Le polymère et/ou l'oligomère enrobe(nt) les particules inorganiques à surface modifiée. L'invention concerne également des dispersions obtenues avec ledit procédé et leur utilisation dans des systèmes de vernis ou d'enduits, ainsi que comme adhésifs ou comme matériaux d'étanchéité.
EP07819836A 2006-12-11 2007-11-16 Procédé de production de dispersions Withdrawn EP2102271A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006058202A DE102006058202A1 (de) 2006-12-11 2006-12-11 Verfahren zur Herstellung von Dispersionen
PCT/EP2007/009935 WO2008071285A1 (fr) 2006-12-11 2007-11-16 Procédé de production de dispersions

Publications (1)

Publication Number Publication Date
EP2102271A1 true EP2102271A1 (fr) 2009-09-23

Family

ID=39086137

Family Applications (1)

Application Number Title Priority Date Filing Date
EP07819836A Withdrawn EP2102271A1 (fr) 2006-12-11 2007-11-16 Procédé de production de dispersions

Country Status (4)

Country Link
US (1) US20100029807A1 (fr)
EP (1) EP2102271A1 (fr)
DE (1) DE102006058202A1 (fr)
WO (1) WO2008071285A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009010670A1 (de) 2009-02-27 2010-09-30 Philipps-Universität Marburg Verfahren zur Herstellung von mit polymeren umhüllten metallhaltigen Nanopartikeln und daraus erhältliche Partikel
DE102009006942A1 (de) 2009-01-30 2010-08-05 Philipps-Universität Marburg Verfahren zur Herstellung von mit Polymeren umhüllten metallhaltigen Nanopartikeln und daraus erhältliche Partikel
JP5585957B2 (ja) * 2010-08-12 2014-09-10 東海カーボン株式会社 ポリウレタン樹脂付加顔料、ポリウレタン樹脂付加顔料の製造方法、顔料分散組成物およびインクジェットインク組成物

Family Cites Families (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19512427A1 (de) * 1995-04-03 1996-10-10 Inst Neue Mat Gemein Gmbh Kompositklebstoff für optische und optoelektronische Anwendungen
EP1320561B1 (fr) * 2000-09-22 2010-03-17 PPG Industries Ohio, Inc. Polyurethanes durcissables, revetements prepares a partir desdits polyurethanes et procede de production de ces elements
CA2474454C (fr) * 2002-01-31 2010-08-03 Dainippon Ink And Chemicals, Inc. Composition de resine styrenique et son procede de production
DE10221007B4 (de) * 2002-05-11 2016-10-13 Basf Coatings Gmbh Wässrige Dispersion von anorganischen Nanopartikeln, Verfahren zu ihrer Herstellung und ihre Verwendung
DE10226932A1 (de) * 2002-06-17 2003-12-24 Bayer Ag Strahlenhärtende Beschichtungsmittel
US7045573B2 (en) * 2003-04-21 2006-05-16 Bayer Materialscience Llc Polyurethane dispersion (PUD) with improved isopropanol resistance, flexibility and softness
DE102004002526A1 (de) * 2004-01-16 2005-08-04 Bayer Materialscience Ag Thermovergilbungsstabile Polyurethan-Polyharnstoff Dispersionen
DE102004013259A1 (de) * 2004-03-18 2005-09-29 Bayer Materialscience Ag Wässrige PUR-Dispersionen mit verbesserter Haftung
US20060014880A1 (en) * 2004-07-14 2006-01-19 Qiping Zhong Nano-talc polymer composites
WO2006008120A1 (fr) * 2004-07-16 2006-01-26 Alberdingk Boley Gmbh Dispersion aqueuse de liant comportant des nanoparticules, et son procede de production et d'utilisation
US7709053B2 (en) * 2004-07-29 2010-05-04 Rohm And Haas Electronic Materials Cmp Holdings, Inc. Method of manufacturing of polymer-coated particles for chemical mechanical polishing

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2008071285A1 *

Also Published As

Publication number Publication date
US20100029807A1 (en) 2010-02-04
DE102006058202A1 (de) 2008-06-12
WO2008071285A1 (fr) 2008-06-19

Similar Documents

Publication Publication Date Title
EP1773919B1 (fr) Dispersion aqueuse de liant comportant des nanoparticules, et son procede de production et d'utilisation
EP1690902B1 (fr) particules nanométriques à surfaces modifiées, procédé de fabrication et utilisation
EP2049603B1 (fr) Particule à surface modifiée et procédé de fabrication
DE102005039436B4 (de) Beschichtungsmassen enthaltend mit Silanen modifizierte Nanopartikel
EP2144968B1 (fr) Nanoparticules dispersibles
EP1922368B1 (fr) Matieres d'enduction contenant des nanoparticules d'oxyde mixte
DE10241510A1 (de) Nanokomposite, Verfahren zu ihrer Herstellung und ihre Verwendung
DE102013224206A1 (de) Oberflächenmodifizierte partikuläre Metalloxide
EP2638114B1 (fr) Dispersion et préparation pour laque contenant des particules hydrofugées de dioxyde de silicium
DE102004040264A1 (de) Partikel mit geschützten Isocyanatgruppen
EP1910461B1 (fr) Peinture contenant des particules
DE102007030285A1 (de) Oberflächenmodifizierte Partikel und Herstellungsverfahren
EP2102271A1 (fr) Procédé de production de dispersions
EP2087036A2 (fr) Compositions contenant des particules à fonction phosphonate
EP1846525A1 (fr) Laque renfermant des particules a groupes isocyanate proteges
EP2089479A2 (fr) Nanoparticules dispersibles
WO2008058678A1 (fr) Matériaux de revêtement contenant une cire d'ester réactive et des nanoparticules d'oxyde mixte
DE102006021705B3 (de) Verwendung von Mischoxid-Nanopartikeln in Beschichtungsmassen
DE102009040488A1 (de) Verfahren zur Herstellung von Dispersionen mit nanoskaligen Siliziumdioxid-Partikeln aus pyrogenen Kieselsäuren
DE102007003435A1 (de) Druckfarbenbeschichtungsmassen enthaltend Mischoxid-Nanopartikel
DE102005026699A1 (de) Lacke enthaltend Partikel mit geschützten Isocyanatgruppen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20090404

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU LV MC MT NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20091012

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20110308