EP1910462A2 - Suspensions de hdk stabilisees destinees a renforcer des resines reactives - Google Patents

Suspensions de hdk stabilisees destinees a renforcer des resines reactives

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Publication number
EP1910462A2
EP1910462A2 EP06764044A EP06764044A EP1910462A2 EP 1910462 A2 EP1910462 A2 EP 1910462A2 EP 06764044 A EP06764044 A EP 06764044A EP 06764044 A EP06764044 A EP 06764044A EP 1910462 A2 EP1910462 A2 EP 1910462A2
Authority
EP
European Patent Office
Prior art keywords
groups
polymer
suspension
particulate
particulate thickener
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Withdrawn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
EP06764044A
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German (de)
English (en)
Inventor
Herbert Barthel
Michael Dreyer
Torsten Gottschalk-Gaudig
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.)
Wacker Chemie AG
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Wacker Chemie AG
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Filing date
Publication date
Application filed by Wacker Chemie AG filed Critical Wacker Chemie AG
Publication of EP1910462A2 publication Critical patent/EP1910462A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/61—Polysiloxanes
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/625—Polymers of alpha-beta ethylenically unsaturated carboxylic acids; hydrolyzed polymers of esters of these acids
    • C08G18/6254—Polymers of alpha-beta ethylenically unsaturated carboxylic acids and of esters of these acids containing hydroxy groups
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • 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
    • 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
    • C09D7/43—Thickening agents
    • 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
    • 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
    • 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
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • the invention relates to a suspension and products made therefrom.
  • Pyrogenic silica exhibits high space filling and strong interparticle interaction, and generates in liquid
  • active fillers which are also particulate thickeners, such as with fumed silica necessary.
  • the object of the invention is to improve the state of the art and in particular to provide flowable systems with at the same time a high proportion of conventional "thickening agents" which also serves as reinforcing filler.
  • Thickeners are bound in the suspension, in which case binding strong physical bonds and chemical bonds encloses, and so the use of finely divided particles, which are also particulate thickener, for reinforcing reactive resins such as adhesives,
  • Coating materials and printing inks by the use of stabilized suspensions according to the invention, such as dispersions, of particulate thickener is made possible.
  • particulate thickeners such as precipitated silica and fumed silica, fumed aluminas and titanium dioxides, as reinforcing fillers at a high degree of filling and thus high reinforcing effect and at the same low viscosity, and thus cost-effective handling and good and easy processing of the suspensions of the invention are used.
  • An object of the invention is a suspension, characterized in that it contains at least 3% by weight, preferably at least 6% by weight, more preferably at least 12% by weight, more preferably at least 15, most preferably at least 18% by weight, most preferably at least 24% by weight of particulate
  • Thickener containing at least one polymer of an amount of at least 5 weight percent, preferably at least 10 weight percent, more preferably at least 20 weight percent, most preferably at least 33 weight percent, more preferably at least 50 weight percent, based on the pure particulate thickener mass without polymer, to this particulate thickener is bound in the suspension, and that optionally at least one further polymer or more polymers is also present in the suspension freely, that the relative viscosity ⁇ re i ⁇ / ⁇ 0 , where ⁇ and T
  • the determination of the amount of particulate thickener bound polymer in the suspension can be accomplished, for example, by filtration of the particulate thickener with fine filters, ultrafine filters with and without pressure, for example by pressure nutsche and submicron fine filters.
  • the filtrate is preferably washed several times with a suitable solvent, preferably 3 times, more preferably 5 times.
  • a suitable solvent is one such that the bound polymer would dissolve well in the unbound state.
  • the filter cake is washed until the wash liquor has less than 1 percent by weight polymer based on the particulate thickener used in the analysis run.
  • Suitable methods for determining polymer bound to inorganic particulate thickener are elemental analysis for carbon content, nitrogen content, silicon content, nuclear magnetic resonance methods such as 1 H-NMR, 13 C-NMR, 15 N-NMR, 29 Si-NMR, and infrared analysis in the different variants such as FTIR, DRIFT, ATIR.
  • o is defined as the ratio of the viscosity ⁇ of the suspension according to the invention contains particulate thickener and the viscosity T
  • the particulate thickeners according to the invention are preferably particulate thickeners which are solid at room temperature and under the pressure of the surrounding atmosphere, ie between 900 and 1100 hPa.
  • the particulate thickeners according to the invention are preferably insoluble or sparingly soluble in water or in other solvents which can be used to prepare the suspension according to the invention.
  • the particulate thickeners according to the invention preferably have a solubility, in water at pH 7.33 and an electrolyte background of 0.11 mol / l and a temperature of 37 0 C, of less than 0.1 g / l, more preferably of less than 0, 05 g / l, at, at the pressure of the surrounding atmosphere, ie between 900 and 1100 hPa.
  • the particulate thickeners used according to the invention preferably have a molecular weight of greater than 10,000 g / mol, more preferably a molecular weight of from 50,000 to 100,000,000 g / mol, in particular from 100,000 to 10,000,000 g / mol, in each case preferably measured by means of static light scattering.
  • the particulate thickeners used according to the invention preferably have a carbon content of less than 50
  • the particulate thickeners according to the invention preferably have a Mohs hardness equal to or greater than 1. Particularly preferably, the particulate thickeners have a Mohs hardness greater than 4, very particularly preferably greater than 5, on.
  • organosilicon resins such as silicone resins such as methyl silicone resins, for example consisting of units of the formula [(CH 3) SiC> 3/2] or Phenylsilikon
  • Main group such as aluminas, oxides of IV.
  • Main group such as silicas, germanium, and the main group, such as antimony oxides, or antimony tin oxides and, for example, oxides of the transition group metals, such as titanium (IV) dioxides, such as zirconium (IV) oxides, such as zinc oxides such as iron oxides, for example, such as ferrous oxides, ferric oxides such as magnetites, ferrites, and oxides of lanthanides such as cerium (IV) oxides; and any mixtures of these oxides, such as silica-alumina mixed oxides of arbitrary composition, preferably containing 20 to 100 weight percent of silica, such as silica-iron (III) oxide mixed oxides of arbitrary composition, preferably having a content of 20 to 100 Weight percent of silica, such as silica-titanium (IV) oxide mixed oxides of any composition, preferably containing 20 to 100 weight percent silica; and insoluble or sparingly soluble ionic
  • Preferred particulate thickeners according to the invention are metal oxides having BET specific surface areas of greater than 10 m 2 / g, such as metal oxides prepared by precipitation processes, such as metal oxides produced in high-temperature processes, such as pyrogenic metal oxides produced in flame processes, such as metal oxides produced in plasma processes, as produced in hot-wall reactors Metal oxides and metal oxides produced by laser processes.
  • Silica particles, silica particles, aluminum oxide particles, titanium dioxide particles, zirconium dioxide particles, metal carbonates, and plastic particles are preferred as particulate thickeners.
  • metal carbonates are preferably precipitated barium carbonates or precipitated calcium carbonates, for example those modified with carboxylic acids and carboxylic acid salts, such as sodium or potassium stearates.
  • particulate thickeners to silicas having BET specific surface areas of greater than 10 m 2 / g, more preferably synthetic silicas, such as wet-chemically prepared silicas, such as, for example
  • Silica sols and silica gels and precipitated silicas such as pyrogenic silicas produced by flame processes, such as silicon dioxides produced in plasma processes, such as silicon dioxides prepared in hot wall reactors, such as silicon dioxides produced in laser processes
  • Fumed silica is preferably prepared at preferred temperatures above 1000 ° C.
  • Particulate thickening agents in the suspension may also be selected from any mixtures of the particulate thickeners listed above.
  • particulate thickening agents have an average diameter of less than 100 .mu.m.
  • the particulate thickeners used according to the invention preferably have an average diameter of greater than 1 nm, preferably from 1 nm to 100 .mu.m, particularly preferably from 10 nm to 10 .mu.m, in particular from 10 nm to 1000 nm.
  • the particulate thickeners preferably have an average primary particle particle size d PP of 0.5 to 1000 nm, preferably 5 to 100 nm, more preferably 5 to 50 nm.
  • d PP average primary particle particle size
  • SAXS small angle X-ray scattering
  • SANS small angle neutron scattering
  • SALS small angle light scattering
  • the total distribution width of all primary particles over all aggregates is preferably greater than 2, more preferably greater than 3, very particularly preferably greater than 5, based on the mean Primary particle diameter of all primary particles.
  • the internal distribution width of the primary particles in an aggregate is less than 5, preferably less than 3, more preferably less than 2, most preferably less than 1.5, wherein the internal distribution width represents the ratio between the largest and smallest primary particle diameter in an aggregate.
  • the particulate thickeners preferably have an average secondary structure or aggregate particle size d Ag gr of 50 to 5000 nm, preferably 100 to 500 nm, measured as the hydrodynamic diameter.
  • Suitable measurement methods for this purpose are, for example, dynamic light scattering or photocorrelation spectroscopy or quasi-elastic light scattering.
  • concentrations greater than 0.01% by weight of particulate thickener this measurement can be corrected for multiple scatter by measuring in backscatter, for example at 170 ° to 175 °, or by cross-correlation.
  • Further examples of aggregate particle size measurement methods are small-angle X-ray scattering
  • SAXS Small Angle Neutron Scattering
  • SANS Small Angle Neutron Scattering
  • SALS Small Angle Light Scattering
  • the total width of all aggregates distribution is greater than 2, more preferably greater than 3, most preferably greater than 5, based on the average aggregate diameter of all aggregates.
  • the quotient of the 97.5% total transit value to the 2.5% total pass value of the total distribution width of all aggregate diameters of all aggregates is preferably greater than 2, particularly preferably greater than 3, very particularly preferably greater than 5, very particularly preferably greater than 10.
  • the particulate thickening agents preferably have an average tertiary or agglomerate particle size d Ag gi of greater than 100 nm, measured as a geometric diameter. Suitable measurement methods for this purpose are, for example, laser light diffraction or sieving methods.
  • the particulate thickeners preferably have a specific surface area of from 1 to 1000 m.sup.2 / g, preferably from 10 to 500 m.sup.2 / g, very particularly preferably from 25 to 350 m.sup.2 / g.
  • the BET surface is measured by known methods, preferably in accordance with German industrial standard DIN 66131 and DIN 66132.
  • the BET specific surface area of the particulate thickeners is 10-150 m 2 / g, more preferably 30-80 m 2 / g.
  • the particulate thickening agents have a fractal dimension of the surface D s of preferably less than or equal to 2.3, preferably less than or equal to 2.1, more preferably from 1.95 to 2.05, the fractal dimension of the surface D s here defined as: Particle surface is proportional to the particle radius R high D s .
  • the particulate thickening agents preferably have a fractal dimension of the mass D m of preferably less than or equal to 2.8, preferably equal to or less than 2.5, particularly preferably 1.9 to 2.2.
  • the fractal dimension of the mass D m is defined as: Particle mass is proportional to the particle radius R high D m .
  • hydrophilic pyrogenic silicas which are freshly prepared and, for example, come directly from the flame, those which have cooled, those which deacidify and are cleaned, those that are stored intermediately or already packaged commercially. It is also possible to use hydrophobized or silylated silicas, for example commercial ones.
  • Mixtures of different silicas may be used, e.g. Mixtures of silicic acids of different BET surface area, or mixtures of silicas with different degree of hydrophobing or Silyliergrad.
  • the particulate thickeners are hydrophobic particulate thickeners.
  • the particulate thickeners are preferably surface-modified
  • Metal oxides wherein the surface-modified metal oxides are preferably silylated organosilicon-modified metal oxides, very particularly preferably surface-modified, preferably silylated, organosilicon-compound-modified, fumed silica.
  • particulate thickeners which are surface-modified organofunctionally.
  • particulate thickeners which are organofunctionally surface-modified with organosilicon compounds
  • particulate thickeners which have been prepared according to EP-A-896 029, EP-A-1302444, EP-A-1304332 and EP-A-1473296.
  • additional densification processes may be used during the silylation or hydrophobization process be used as compression by suction of the air or gas content by suitable vacuum methods, such as compaction by mechanical methods, such as press rolls, ball mills, edge mills, screw compressors and briquetting.
  • deagglomeration processes may additionally be employed during the silylation or hydrophobization process, such as pin mills or refining devices.
  • the tap density can be determined according to DIN EN ISO 787-11. Particular preference is given to particulate thickeners having tamping densities according to DIN EN ISO 787-11 of tapped densities greater than 60 g / l, particularly preferably greater than 120 g / l, very particularly preferably greater than 250 g / l, in particular greater than 500 g / l.
  • particulate thickening agents form the aggregates of a porosity> 0.5, especially> 0.8, in particular> 0.9, in particular> 0.95.
  • particulate thickeners are nanoparticles.
  • the particulate thickener and particle-bound polymer in the liquid preferably form a colloidal suspension.
  • Colloidal suspension of particulate thickeners means in this case that the transparency of the suspension, measured as a continuous light, ie unabsorbed light, is not less than 50%, preferably less than 25%, more preferably less than 10% than that of the particle-free liquid or crosslinked mass ,
  • the particulate thickening agents are preferably distributed colloidally in the suspension.
  • the colloidal distribution of the particulate thickening agents in the suspension is indicated by a high transparency of the suspension.
  • the transparency is preferably greater than 50%, preferably greater than 75%, particularly preferably greater than 90%, based on the suspension or liquid not containing particulate thickener or crosslinked mass prepared therefrom.
  • particulate thickener is mixed in the monomer, oligomer, polymer or resin and dispersed and thereby dispersed and suspended, preferably under the action of shear energy, such as mechanical or ultrasonic shear, for example, are used for predispersion and also for main dispersion dissolver.
  • shear energy such as mechanical or ultrasonic shear, for example.
  • the dispersing effect of the dissolver is determined by the differential speed between the disk surface and
  • the settings of the slots in the stator can be adapted to the task.
  • Manufacturer is for example the company Y-ray.
  • For the dispersion for example: 3 rolls, in particular for the production of pasty, printing inks; Ball mills, which are used with steel and ceramic balls (20 -30mm diameter) in certain proportions to the material to be ground and agitator ball mills.
  • Description of a stirred ball mill In a grinding pot, which is filled with sand or grinding beads, a stirring shaft rotates with grinding discs. The ground material is pumped from below or even in horizontal mills from the end face through the grinding pot, for example.
  • the grinding media used are generally sand, hard glass balls and preferably ceramic grinding beads of 0.1 to 3.0 mm.
  • the millbase viscosity is these aggregates typically at a viscosity of 0.5 to 4 Pa * s at 25 0 C.
  • ultrasound-based dispersing for example, ultrasonic tips, sonolators, ultrasound cells with one or more ultrasonic transducers or one or more Sonotrodes or one or more ultrasonic horns, which can be operated discontinuously or continuously in flow, used.
  • Particularly preferred dispersing aggregates such as HIGH PRESSURE HOMOGENIZER and WET JET MILLS offer the possibility of an increased
  • dispersing aggregates which are introduced into the dispersant by vigorous shaking, such as Red Devil or Speedmixer Engerie, or Planetary mixers or planetary dissolvers, or for example for systems with high viscosity, for example over 10 Pa * s at 25 0 C, roll mills, kneaders, internal mixers, extruders, such as single extruder, twin screw extruder, preferably according to the invention is a combination of one or more methods , and thereby the particulate thickener is dispersed and suspended.
  • the dispersion, oligomer, polymer or resin described above preferably "in situ”, chemisorptively binds to particulate thickener, ie achieves a chemical reaction between oligomer, polymer or resin and particulate thickener, or physico-reactive oligomer, polymer or resin bonded to particulate thickener.
  • the suspension of the particulate thickener in the liquid is stable.
  • stable means that, after a time greater than 100 hours, sedimentation of the particulate thickening agents of less than 10%, preferably less than 5%, particularly preferably less than 1%, of the total mass of particulate thickener occurs.
  • Stable means, according to another method of measurement, that no gelling, no stability or no strain occurs.
  • No gelling can be determined by fluidity, even at rest and without external shear.
  • No stability, ie flowability means that even at low shear stress, the viscous fraction, the loss modulus G "of the viscoelastic suspension, is greater than the elastic fraction, the storage modulus G 'of the Viscoelastic suspension is preferably measured at a shear stress less than 1 Pa or at a deformation less than 1 percent.
  • o, less than 100, preferably less than 50, more preferably less than 10, most preferably 5, more preferably less than 3, outstanding preferably less than 2 and the relative viscosity ⁇ re i ⁇ / ⁇ o with a storage of at least one week, preferably of at least 4 weeks, more preferably of at least 3 months, most preferably of at least 6 months, more preferably of at least 12 months, at a temperature of 4O 0 C by less than a factor of 10, preferably by less than a factor of 10, preferably by less than a factor of 5, more preferably by less than a factor of 2.5, even more preferably by less than a factor of 1.5.
  • the liquid phase is a flowable material having a viscosity of 0.1 to 100,000 Pas
  • the liquid phase may preferably contain solvents, such as inert and reactive, nonpolar and polar, protic and non-protic solvents.
  • Solvents may in pure form have a viscosity of less than 100 mPas at 25 0 C, preferably less than 10 mPas, more preferably less than 2 mPas.
  • reactive solvents are preferably reactive diluents, such as monostyrene; such as monoacrylates, such as alkyl acrylates, for example methyl acrylate, such as alkyl alkyl acrylates, such as methyl methacrylate, or Hexyl methacrylate, or oligoalkyl alkyl acrylates, or glycidyl ethers, such as allyl glycidyl ether.
  • monostyrene such as monoacrylates, such as alkyl acrylates, for example methyl acrylate, such as alkyl alkyl acrylates, such as methyl methacrylate, or Hexyl methacrylate, or oligoalkyl alkyl acrylates, or glycidyl ethers, such as allyl glycidyl ether.
  • inert and non-polar solvents are preferably aliphatic hydrocarbons, such as cyclic, linear and branched saturated hydrocarbons, such as hexanes, such as n-hexane, or cyclohexane, or deans, such as n-decane, and cyclic, linear and branched unsaturated hydrocarbons, such as hexene, and are aromatic hydrocarbons such as benzene, toluene or xylene, and mixtures of hydrocarbons such as gasoline, such as mineral spirits, such as higher boiling hydrocarbons.
  • aliphatic hydrocarbons such as cyclic, linear and branched saturated hydrocarbons, such as hexanes, such as n-hexane, or cyclohexane, or deans, such as n-decane
  • cyclic, linear and branched unsaturated hydrocarbons such as hexene
  • aromatic hydrocarbons such as benzene, toluen
  • protic solvents is water.
  • protic solvents are preferably alcohols, such as alkyl alcohols, such as methanol, such as ethanol, such as propanols, such as n-propanol and isopropanol, such as butanols.
  • alkyl alcohols such as methanol, such as ethanol
  • propanols such as n-propanol and isopropanol, such as butanols.
  • polar and non-protic solvents are preferably ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethers, such as diethyl ether, tetrahydrofuran, dioxane, and amides, such as dimethylformamide.
  • the liquid phase may preferably contain polymers, oligomers, and resins, individually or as any mixtures.
  • the liquid phase may contain a plurality of polymers, a plurality of oligomers, and a plurality of resins, individually or as any mixtures.
  • Polymer is a compound made up of greater than 3 subunits of a monomer.
  • Polymers, oligomers, and resins preferably have a molecular weight of 100 to 10,000,000 mol / g, especially preferably 500-50,000 mol / g, most preferably 500-5,000 mol / g.
  • Polymers, oligomers, and resins may preferably be linear, cyclic, or branched, or mixtures of polymers.
  • polymers are preferably organosilicon compounds, such as organo (poly) silanes, organo (poly) siloxanes, such as dialkylpolysiloxanes, for example polydimethylsiloxanes, and copolymers thereof, such as polydimethylsiloxane-polyurethane copolymers, obtainable as reaction products of ⁇ , G0-amino-terminated polydimethylsiloxanes and Alkylisocyanaten (available from Wacker-Chemie GmbH under the name Geniomer ® ), such as
  • Organo (poly) silazanes and organo (poly) silicarbanes such as Organo (poly) silazanes and organo (poly) silicarbanes; Polyolefins such as polyethylenes and polypropylenes, for example, substituted polylefins such as silyl-terminated polyisobutylenes; Polyurethanes, polyols, such as hydroxyl-containing polyesters, hydroxy-containing polyether, methyldimethoxysilylpropyl-terminated
  • Polypropylene glycols available, for example, as "MS polymers” from the company Kaneka Corp. Japan
  • polyisocyanates such as aliphatic and aromatic polyisocyanates
  • isocyanate-terminated polyurethane prepolymers prepared by reacting polyols with polyisocyanates in excess and their silyated derivatives (eg available under the name DESMOSEAL® from Bayer AG, Germany);
  • (poly) epoxy compounds such as bisphenol A and bisphenol F based epoxides, compounds containing monomeric, oligomeric and polymeric glycidoxy functions, such as diglycidyl ethers based on Bisphenol A and bisphenol F, epoxy novolac precursors and resins, epoxyalkyd resins, epoxy acrylates, aliphatic epoxides such as linear alkylene bisglycidyl ethers and cycloaliphatic glycidyl ethers, such as 3,4-epoxycyclohexy
  • polymers are preferably film-forming polymers.
  • film-forming polymers are physical drying paint binders, such as e.g. Polyvinyl chloride and its copolymers, polyacrylates and their copolymers, polyvinyl acetates and polyvinyl butyrals and their copolymers, bitumen, hydrocarbon resins; Chlorinated rubbers, cyclic rubber, polyurethanes, epoxy resins, epoxy resins-polyester.
  • Preferred according to the invention are reactive polymers, reactive oligomers, and reactive resins.
  • Preferred examples are reactive polymers, prepolymers, reactive precursors, polymers which can be used as binders, for example for paints and varnishes, adhesives and sealants, or for elastomers and plastic plastics, and which interact with themselves or with the particulate thickeners , react or network.
  • Preferred reactive polymers are resin and hardener systems, such as those used for the preparation of resins and elastomers, such as for epoxy resins and elastomers, for polyurethane resins and elastomers, for silicone resins and elastomers, and for acrylates, such as for polyolefins. as for
  • Polycarbonates as for polysulfones, as for polysulfides, and as for polyamides.
  • polymers and reactive polymers are preferably organic polymers, such as polymers, such as poly (meth) acrylates, such as polyvinyl esters, such as polyvinyl alcohols, such as
  • Polyvinyl acetals such as polyvinyl chloride, such as polyfluorinated polyethylenes, with monomeric starting components such as methyl methacrylate, butyl acrylate, ethylhexyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, acrylic acid, styrene.
  • polymers and reactive polymers are preferably organic polymers, such as polycondensation resins, such as oil-free saturated polyesters and oil-modified polyester resins, such as fatty oils, short-, medium- and long-oil alkyd resins,
  • modified alkyd resins such as styrene-modified alkyd resins, acrylic acid ester-modified alkyd resins, silicone-modified alkyd resins, urethane-modified alkyd resins, epoxy resin-modified alkyd resins such as oxidatively drying
  • Paint binders such as short. Medium and long oil alkyd resins, oil cakes, and combinations thereof, and polyesters.
  • polymers and reactive polymers are preferably organic polymers such as chemically or reactively drying Paint binders, such as polyurethanes, such as 1-component and 2-component polyurethanes, such as epoxy resin system, such as 2-component epoxy resin systems, such as epoxies, which are crosslinked with amines, and those which are crosslinked with isocyanates.
  • Paint binders such as polyurethanes, such as 1-component and 2-component polyurethanes, such as epoxy resin system, such as 2-component epoxy resin systems, such as epoxies, which are crosslinked with amines, and those which are crosslinked with isocyanates.
  • polymers and reactive polymers are preferably silicon-containing polymers, such as polysiloxanes, such as polyorganosiloxanes, such as linear or cyclic dialkylsiloxanes having an average number of dialkylsiloxy units greater than 3.
  • the dialkylsiloxanes are preferably dimethylsiloxanes.
  • linear polydimethylsiloxanes having the following end groups: trimethylsiloxy-, dimethylhydroxysiloxy-, dimethylchlorosiloxy-, methyldichlorosiloxy-, dimethylmethoxysiloxy-, methyldimethoxysiloxy-, dimethylethoxysiloxy-, methyldiethoxysiloxy-,
  • the abovementioned polydimethylsiloxanes preferably have a viscosity at 25 ° C. of from 20 to 10,000,000 mPas, more preferably from 100,000 mPas to 10,000,000 mPas, very particularly preferably from 1,000,000 to 10,000,000 mPas.
  • organosiloxanes are preferred.
  • Silicone resins in particular those which contain, as the alkyl group R are methyl groups (CH 3) which is particularly preferred are those which contain the R3SiO ⁇ / 2 and SiO 4/2 ⁇ units or those RSiC> 3/2 and optionally R2SiC> Contain 2/2 ⁇ units, wherein R is hydrogen or saturated or unsaturated optionally substituted hydrocarbon radical having 1 to 12 carbon atoms.
  • R is hydrogen or saturated or unsaturated optionally substituted hydrocarbon radical having 1 to 12 carbon atoms.
  • the organosiloxanes may each be a single species as well as a mixture of at least two species act such substances.
  • polymers are preferably silicone oils, such as organofunctional silicone oils, particularly preferably aminoalkyl-functional polysiloxanes, polymethylsiloxanes and
  • Polydimethylsiloxanes are silicone resins, particularly preferably organofunctional silicone resins, particularly preferably aminoalkyl-functional silicone resins.
  • Preferred examples are silicone copolymers, and hybrid systems containing organopolysiloxanes and silicon atom-free polymers.
  • Preferred examples of the present invention are thermoplastic silicone elastomers characterized by .alpha.,. Omega.-terminal termination with 3-aminoalkyldialkylsiloxy radicals such as 3-aminopropyldimethylsiloxy radicals and a degree of
  • thermoplastic silicone elastomers preferably have a siloxane content of greater than 80 percent by weight, preferably greater than 90 percent by weight, and are preferably solid at 25 ° C. and have a viscosity of from 10,000 to 100,000 Pas at a temperature of HO 0 C.
  • polydimethylsiloxanes are preferably polymers for the preparation of silicone rubbers, such as polymers for the preparation of 1-component or 2-component
  • a catalyst such as platinum, palladium or ruthenium
  • Examples of condensable groups siloxane is organopolysiloxane, preferably containing units of the formulas SiO 4/2 , R3SiO 1/2 , R2SiO 2/2 and RSiO 372 , wherein R is hydrogen or saturated or unsaturated optionally substituted hydrocarbon radical having 1 to 12 carbon atoms is.
  • Example of silicone resins are preferably those which consist of RSiC> 3/2, RsSiOi / 2 and SiC> a 4/2 units wherein R is hydrogen or saturated or unsaturated optionally substituted hydrocarbon radical having 1 to 12 carbon atoms, in any combination preferably with molecular weights of 100 to 20,000 grams per mole, and a viscosity of 50 to
  • silicone resins 50000 mPas at a temperature of 25 ° C. or, if the silicone resins are solids, at a viscosity of the 0.1 to 50% strength by weight solution of the silicone resins in an inert solvent, such as toluene, tetrahydrofuran, methyl ethyl ketone or isobutylene glycol.
  • an inert solvent such as toluene, tetrahydrofuran, methyl ethyl ketone or isobutylene glycol.
  • Preferred examples are methyl silicone resins and phenyl silicone resins and methyl phenyl silicone resins.
  • reactive polymers according to the invention are preferably silane-terminated, silane-functional and organosilane-modified polymers, such as Polymers containing mono-, di- and tri-alkoxysilane radicals, terminal, or linked in the chain.
  • silane-terminated polymers prepared via the reaction of aminoalkylalkoxysilane and mono-, di- and / or polyisocyanates, or by copolymerization of
  • Methacryloxyalkylsilanes and acrylates or alkylacrylates also with mixed copolymerization with other olefins, such as styrenes, such as monostyrene, alkoxysilane-functional polyols prepared by hand, or by reaction of alkoxysilanes with polyols, such as polyacrylate polyols,
  • Polyester polyols or polyether polyols as used for the production of polyurethanes.
  • the silane termination of polyacrylate polyols can be carried out by copolymerization with methacryloxy-functional alkoxysilanes, such as 3-methacryloxypropyltrimethoxysilane or preferably with 1-methacryloxymethyltrimethoxysilane.
  • silane termination of polyisocyanates can be carried out by reaction with amino-functional alkoxysilanes, such as 3-aminopropyltrimethoxysilane or preferably with 1-piperazinomethyltrimethoxysilane.
  • amino-functional alkoxysilanes such as 3-aminopropyltrimethoxysilane or preferably with 1-piperazinomethyltrimethoxysilane.
  • reactive polymers which are preferred according to the invention are preferably epoxy-functional or glycidoxy-functional monomers, oligomers or polymers, such as epoxide resins, such as diglycidyl ether of bisphenol A, cycloaliphatic epoxides, as used, for example, for producing epoxy adhesives, composites, glass-fiber-reinforced epoxides. Plastics and epoxy surface coatings are used.
  • epoxides are preferably epoxy resins, such as liquid, semi-solid, solid epoxy resins, epoxy resins consisting for example of binders, bisphenol A and / or bisphenol F and phenol novolak glycidyl ether, cresol novolak glycidyl ether, cycloaliphatic glycidyl compounds and epoxidized cycloolefins and hardeners based on aliphatic amines, such as polyfunctional amines based on
  • Polyetherpolyamines alkylenediamines, such as propylenediamines, or cycloaliphatic amines, polyaminoamides, Mannich bases, epoxide adducts, mercaptans, acid anhydrides.
  • epoxy compounds are preferably cycloaliphatic epoxides, and alkylene bisglycidyl ethers, such as
  • Bisphenol A based di-glycidyl ethers such as
  • n preferably from 0 to 10, particularly preferably 0 to 5
  • epoxy novolac resins such as those of the formula
  • bifunctional epoxy compounds such as cycloaliphatic epoxy compounds
  • reactive polymers which are preferred according to the invention are preferably amino-functional polymers, oligomers or monomers, such as polyalkylene oxides, which are amino-functional, such as Jeffamine, as used, for example, for producing elastic and semi-elastic epoxy adhesives, composites, glass-fiber-reinforced epoxy resins. Plastics and epoxy surface coatings used as a hardener.
  • reactive polymers are preferably amino group-containing monomers, oligomers, polymers and resins, such as hardeners for epoxy systems or hardeners for polyurethane systems, or hardeners for moisture-curing 1-component silicone adhesives and sealants, or leveling and flow aids, For example, be used as additives in coating systems, or mixtures thereof.
  • polymers are preferably unsaturated polyester resins derived from di-, tri-, and mono- or polyfunctional carboxylic acids and their anhydrides, such as phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic anhydride, tetrahydroxophthalic anhydride, hexahydroxoterephthalic acid, adipic acid, maleic acid, fumaric acid, azelaic acid, sebacic acid , Decanedicarboxylic acid, dimerized fatty acids, trimellitic anhydride, pyromellitic anhydride, 1,4-cyclohexanedicarboxylic acid, dimethylolpropionic acid and mono- or polyhydric alcohols, such as polyols, such as ethylene glycol, 1,2-propanediol, 1,5-pentanediol, diethylene glycol, 1, 4- Butanediol, 1, 6-hexaned
  • Benzoguanamine consist of amino compounds such as aromatic amines, carboxylic acid amides, cyanamides, guanamines, guanediamines, ureas, sulfonamines, Sulfurylamiden, thioureas, triazines (melamine resins),
  • Urethanes and carbonyl compounds such as, acetaldehyde, acetone,
  • polymers and reactive polymers according to the invention are preferably polyaddition resins such as polyurethanes, such as, for example, 2-component polyurethanes, 1-component polyurethanes, 1-component moisture-curing polyurethanes obtained from prepolymers such as polyisocyanates, prepared from base products such as aromatic diisocyanates such as toluene diisocyanate, methylene diphenyl diisocyanate, xylene diisocyanate, aliphatic diisocyanates such as hexamethylene diisocyanate or hexyl diisocyanate, cycloaliphatic diisocyanates, and the isomeric mixtures of the respective diisocyanates listed, blocked or protected polyisocyanates based on typical blocking agents such as malonic esters and acetoacetic esters, secondary amines, Butanone oximes, phenols, caprolactams, alcohols.
  • polyurethanes such as, for example,
  • the suspension preferably contains at least one polymer which is physisorptively bound to one or more particulate thickening agents.
  • the polymers may be physisorptive via preferably van der Waals forces, such as London's fluctuating dipoles or dispersion energy, Debye dipoles, Keesoms-induced dipoles, hydrogen bonds, or hydrogen bonds, especially between -OH, -NH, - SH, -CO, -F, -Cl groups on the one hand, and -OH, -NH, -SH groups on the other, as well as coordinative, ionic, and ionic Lewis acid-base bonds, Brönsted acid-base bonds, and interactions between electrophilic and nucleophilic groups bound.
  • van der Waals forces such as London's fluctuating dipoles or dispersion energy, Debye dipoles, Keesoms-induced dipoles, hydrogen bonds, or hydrogen bonds, especially between -OH, -NH, - SH, -CO, -F, -Cl groups on the one hand, and -OH, -NH, -SH groups on the other, as well as co
  • polymers attached to particulate thickener preferably contain carboxyl groups which may be end-capped and / or pendant in the polymer, preferred examples being polyesters preferably containing such carboxyl groups conjugated to unsaturated olefinic groups, further preferred examples Polymers containing oxygen ether atoms that exhibit nucleophilicity or weak basicity.
  • the suspension preferably contains basic oxygen atoms bound to particulate thickener.
  • polymers for this are polyalkylene oxides, polyols, polyesters.
  • Preferred examples are polyesters, for example those which can be crosslinked with melamine.
  • Further preferred examples of polymers are polyols, such as polyester polyols, polyacrylate polyols, polyalkylene oxide polyols, as are used, for example, for the preparation of 1- and 2-component polyurethanes.
  • physisorptively bound to particulate thickener polymers are coating additives and flow control agents, for example, polyalkylene oxide-modified polydialkylsiloxanes, particularly preferred
  • Polydimethylsiloxanes Preferred examples are ⁇ , G0 terminal, or chain, or linear or branched, or copolymers, or block or block copolymers, propylene group bonded, polyethylene oxide and polypropylene oxide modified polydimethylsiloxanes, wherein one C atom of the propylene group on Si atom of the siloxane and another C atom of the propylene group is bonded to an O atom of the polyalkylene oxide.
  • the polyalkylene oxide-modified polydialkylsiloxanes have a viscosity at 25 0 C of 100 to 100,000 mPas, particularly preferably from 500 to 5,000 mPas, and are used in amounts based on the particulate thickeners of preferably 0.1 to 10 weight percent, more preferably from 0 , 5 to 2.5 weight percent used.
  • the suspension preferably contains greater than 3% by weight, preferably greater than 12% by weight, more preferably greater than 15% by weight and most preferably greater than 18% by weight of particulate thickener, preferably fumed silica with a BET specific surface area greater than 150 m 2 / g. If the particulate thickener contains a fumed silica having a BET specific surface area of less than 150 m 2 / g, then the suspension contains greater than 20 percent by weight, more preferably greater than 30
  • the relative viscosity ⁇ re i is less than 100, preferably less than 50, particularly preferably less than 10, very particularly preferably less than 5, in particular preferably less than 3 and outstandingly preferably less than 2.
  • the suspension preferably contains at least one polymer chemisorptively bound to one or more particulate thickening agents.
  • the suspension contains at least one polymer which is chemisorptively bound to said particulate thickener, said particulate thickener being provided by partial or total surface modification with surface groups which chemically react with the polymer.
  • the suspension contains at least one polymer which is chemisorptively bound to this particulate thickener, this particulate thickener being provided with organofunctional siloxy groups by partial or complete silylation, prepared for example according to EP-A-896 029, EP-A-1302444, EP-A-1304332, and EP-A-1473296, and which chemically react with the polymer.
  • the polymers On the surface of the particulate thickener, the polymers may be bound chemisorptively via at least one bond per polymer molecule, preferably bound over several bonds per polymer molecule.
  • the suspension contains various polymers which are preferably bound to one or more particulate thickening agents chemisorptive and physisorptive, or else as a mixture of these types of binding.
  • Polymer bound to particulate thickener can be prepared by surface modification of particulate thickener with polymer.
  • the polymer bound to the particulate thickener may preferably be prepared by "in situ" surface modification of a particulate thickener with a polymer.
  • "In situ" surface modification of particulate thickener with polymer means that particulate thickener is dispersed in polymer, or polymer mixture or in polymer solvent mixture and thereby or during dispersion or after dispersion, the polymer is bound to particulate thickener, chemically or physically
  • the chemical or physical distinction is given by the binding energy of a single molecular binding site: below 70 kcal per mole there is a physical bond, above 70 kcal per mole there is chemical bonding.
  • the polymer is preferably bound in the suspension to particulate thickener by high shear energy dispersing according to the invention, as described above
  • high shear energy Preparation of the suspension according to the invention under the action of high shear energy, of optionally reactive particulate thickeners which may contain, for example, reactive organofunctional siloxy or alkylsiloxy groups, for example prepared according to EP-A-896 029, EP-A-1302444, EP-A- 1304332, and EP-A-1473296 in optionally reactive polymers, for example as described above under reactive polymers.
  • Thickener greater than 10 parts of polymer, preferably greater than 20 parts, more preferably greater than 50 parts, most preferably greater than 100 parts of polymer bound.
  • the suspension preferably contains at least one polymer chemisorptively bound to these particulate thickeners, this particulate thickener preferably epoxy groups, amino groups, mercapto groups, acrylate groups, isocyanate groups, protected isocyanate group, carboxylic anhydride groups or Carbinol groups which react chemically with the polymer.
  • this particulate thickener preferably epoxy groups, amino groups, mercapto groups, acrylate groups, isocyanate groups, protected isocyanate group, carboxylic anhydride groups or Carbinol groups which react chemically with the polymer.
  • the respective chemical groups may be present alone or in any mixtures with each other.
  • suspension according to the invention is preferably epoxy-functionalized particulate thickener, preferably silica, more preferably fumed silica, in amino-containing monomers, oligomers, polymers and resins, such as hardeners for epoxy systems, or hardeners for polyurethane systems , or harder for moisture-crosslinking 1-component silicone adhesives and sealants, or leveling and flow aids in coating systems, for example as additives, or mixtures thereof, is suspended, as above and, according to the invention, a chemical reaction, preferably "in situ", of the primary (-NH 2 ) or secondary (-NH) amino group of the polymer with the surface-bound epoxy groups of the particulate thickener takes place.
  • a chemical reaction preferably "in situ" of the primary (-NH 2 ) or secondary (-NH) amino group of the polymer with the surface-bound epoxy groups of the particulate thickener takes place.
  • the particulate thickener preferably fumed silica
  • the particulate thickener is preferably epoxy-functional surface-functionalized metal oxide or silica, preferably pyrogenic silica prepared, for example, in EP-A-896,029, EP-A-1302444, EP-A-1304332 and EP-A-1473296.
  • the suspension according to the invention preferably comprises particulate thickening agents, such as preferably metal oxides, preferably silica, particularly preferably fumed silica, which are fully or partially surface-functionalized with epoxy groups, ie only 10-90%, preferably 25-75% of the surface and surface silanol groups with epoxy groups. Silane are implemented.
  • particulate thickening agents such as preferably metal oxides, preferably silica, particularly preferably fumed silica, which are fully or partially surface-functionalized with epoxy groups, ie only 10-90%, preferably 25-75% of the surface and surface silanol groups with epoxy groups. Silane are implemented.
  • the suspension according to the invention preferably contains at least 3% by weight, preferably from 3 to 50, particularly preferably from 3 to 25, in particular preferably from 10 to 20% by weight of particulate thickener, preferably pyrogenic silica.
  • the dispersing of the particulate thickener, preferably fumed silica can be carried out in the presence of a solvent, in a ratio of 0.1 to 10 to the system polymer and particulate thickener;
  • the dispersion can also be carried out without solvent, for sealing and adhesive systems preferred without solvent, for coating systems preferably with solvent.
  • the suspension according to the invention preferably contains greater than 5, preferably greater than 10, particularly preferably greater than 15 and very preferably greater than 18 percent by weight of particulate thickener, preferably metal oxide, more preferably silica, most preferably fumed silica which functionalises epoxy groups and has a BET specific surface area greater than 150 m 2 / g.
  • the suspension according to the invention contains, based on amino-containing polymers, greater than 10, preferably greater than 15, particularly preferably greater than 25 and very particularly preferably greater than 35 percent by weight of a particulate thickener, preferably metal oxide, particularly preferably silica, very particularly preferably fumed silica which surface-functionalizes epoxy groups and has a BET specific surface area smaller than 150 m 2 / g.
  • a particulate thickener preferably metal oxide, particularly preferably silica, very particularly preferably fumed silica which surface-functionalizes epoxy groups and has a BET specific surface area smaller than 150 m 2 / g.
  • the particulate thickeners which can be isolated from the suspension according to the invention preferably fumed silica, preferably have a carbon content of greater than 2, preferably from 3 to 50 and more preferably from 5 to 50 percent by weight.
  • the isolatable from the suspension of the invention particulate thickener preferably fumed silica, have a content of preferably extractable by means of tetrahydrofuran components of greater than 5, preferably 5 to 100 and particularly preferably from 10 to 50 weight percent.
  • the suspension preferably contains at least one polymer which contains epoxy groups and preferably the particulate thickener contains amino groups, mercapto groups, carboxylic anhydride groups and carbinol groups, where the respective group may be present alone or in any desired mixtures which chemisorptively bind the polymer.
  • the suspensions preferably contain particulate thickening agent, preferably with
  • Amino groups preferably aminoalkyl groups
  • this particulate thickener partially or completely, preferably in "in-situ” processes, epoxy-functional or glycidoxy-functional monomers, oligomers or polymers, such as epoxy resins, are reacted
  • Example according to the invention by reacting silica-functionalized, preferably fumed silica functionalized with amino groups, in an epoxy-functional monomer, oligomer, polymer or resin and dispersed as described above to prepare the suspension according to the invention, preferably under the action of high shear energy such described above, or by combination of one or more of the methods described above, and thereby dispersed and suspended, and according to the invention, preferably "in situ", a chemical reaction of the epoxy groups of the epoxy monomer as described above, Oligomer, polymer or resin with the amino groups of the particulate thickener, preferably fumed silica, so for example one of the typical epoxy-amine crosslinking reactions.
  • the particulate thickeners preferably fumed silica, preferably contain from 1 to 50% by weight, particularly preferably from 1 to 20% by weight, particularly preferably from 5 to 15% by weight surface-bound amino groups, such as aminoalkylsiloxy groups, such as primary, -NH 2, and secondary, -NH, amino groups.
  • surface-bound amino groups such as aminoalkylsiloxy groups, such as primary, -NH 2, and secondary, -NH, amino groups.
  • the suspension contains greater than 3 percent by weight, preferably from 3 to
  • particulate thickener preferably fumed silica.
  • the dispersing of the particulate thickener, preferably fumed silica can be done in the presence of a solvent, in a ratio of 0.1 to 10 to the bulk polymers and particulate thickeners;
  • the dispersion can also be carried out without solvent, for sealing and adhesive systems preferably without solvent, for coating systems preferably with solvent.
  • suspensions preferably contain particulate thickener which has silanol groups and siloxane groups and to which monomers, oligomers or polymers, such as polyols, such as acrylate polyols, such as polyester polyols, such as polyether polyols, can be bound physisorptively.
  • the suspension contains greater than 3 percent by weight, preferably from 3 to 50, particularly preferably from 3 to 25 percent by weight, in particular preferably from 10 to 20
  • Weight percent particulate thickener preferably fumed silica.
  • the dispersing of the particulate thickener preferably fumed silica, can be carried out in the presence of a
  • Solvent in the ratio 0.1 to 10 to the mass of polymers and particulate thickeners;
  • the dispersion can also be carried out without solvent, for sealing and adhesive systems preferably without solvent, for coating systems preferably with solvent.
  • the suspension preferably contains at least one polymer containing isocyanate groups and wherein the particulate thickener silanol, siloxane, amino, and carbinol groups, wherein the respective group may be present alone or in any mixtures with each other, chemisorptive with the polymer tie.
  • suspensions preferably contain particulate thickener which is preferred with amino groups Aminoalkyl weakness is functionalized and to this particulate thickener, partially or completely, preferably in "in-situ” processes, isocyanate-functional or protected isocyanate-functional monomers, oligomers or polymers, such as isocyanate-functional polymers, the
  • Preparation of 1- and 2-component polyurethanes are reacted.
  • This can be done, for example, according to the invention by mixing and dispersing silica-functionalized silicic acid, preferably fumed silica functionalized with aminoalkyl groups, into an isocyanate-functional monomer, oligomer, polymer or resin, preferably under the action of high shear energy as described above, or a combination by one or more of the methods described above, and thereby dispersed and suspended, and according to the invention, preferably "in situ", a chemical reaction of the isocyanate groups of the isocyanate monomer, oligomer, polymer or resin as described above with the Amino groups of the particulate thickener, preferably fumed silica prepared according to EP-A-1304332 takes place, that is, for example, a typical isocyanate-amine or urethane crosslinking reactions.
  • the particulate thickeners preferably fumed silica, preferably contain from 1 to 50% by weight, particularly preferably from 1 to 20% by weight, more preferably from 5 to 15% by weight surface-bound amino groups, such as aminoalkylsiloxy groups, such as primary -NH 2, and secondary, -NH, amino groups , Particular preference is given to particulate thickeners, preferably metal oxides, particularly preferably pyrogenic silica, which are partially surface-functionalized with amino groups, ie only 10-90%, preferably 25-75% of the surfaces, preferably surface silanol groups, are reacted with aminosilane.
  • the suspension contains from 3 to 50 percent by weight particularly preferably from 3 to 25% by weight, in particular preferably from 10 to 20% by weight, of particulate thickening agents, preferably pyrogenic silica.
  • particulate thickening agents preferably pyrogenic silica.
  • the dispersing of the particulate thickener, preferably fumed silica, can be carried out in the presence of a
  • Solvent in the ratio 0.1 to 10 to the mass of polymers and particulate thickeners;
  • the dispersion can also be carried out without solvent, for sealing and adhesive systems preferably without solvent, for coating systems preferably with solvent.
  • the suspension preferably contains at least one polymer which preferably contains amino groups and a particulate thickener which has silanol groups, carbinol groups and carboxylic acid groups, it being possible for the respective groups to be present alone or in any mixtures which bind the polymer in a physisorptive manner.
  • Preferred according to the invention is a suspension which contains particulate thickening agents, which preferably carries acidic groups, such as acidic metal, metalloid and
  • Non-metal hydroxide groups such as -OH groups, such as B-OH, P-OH, Al-OH, Si-OH, Ge-OH, Zr-OH groups, particularly preferably silanol groups (Si-OH) of the silica surface, particularly preferably silanol groups of the fumed silica surface , and containing on the surface of particulate thickener polymers having basic groups, such as amines, such as primary, secondary and tertiary amines, such as polymers bearing amino groups, such as primary, secondary or tertiary amines, such as alkylene di-, tri- and Polyamines, such as amino group-containing polyalkylene oxides, such as Jeffamine, or aliphatic or arylaliphatic polyamines and polyamidiamines, aminosiloxanes, such as linear and branched aminosiloxanes, such as liquid and solid aminosiloxanes, such as aminosiloxane polymers or resins, for example polydimethyls
  • Particularly preferred according to the invention are primary, secondary and tertiary amino alcohols and their esters with mono-, di- and polycarboxylic acids.
  • Preferred examples of amino alcohols are cyclic amino alcohols such as piperidine alcohols such as 4-piperidine alcohols.
  • Preferred examples of carboxylic acids are dicarboxylic acid having 2 to 24 carbon atoms, more preferably 4 to 12 carbon atoms.
  • piperidinyl sebacates such as, for example, piperdinylesterified O, G0-dicarboxylic acids, particularly preferably bis-1,2,2,6,6-pentamethyl-4-piperidinyl-sebacate or methyl-1,2,2,6,6 Pentamethyl-4-piperidinyl-sebacate), and mixtures thereof, which are used as liquid light stabilizers (HALS: hindered-amine light stabilizer)).
  • HALS hindered-amine light stabilizer
  • a suspension which contains particulate thickening agents, particularly preferably fumed silica, preferably those containing SiOH groups, and basic polymer containing basic particulate thickeners, such as aminopolysiloxane, such as polydimethylsiloxanes having terminal or in the chain bonded to an Si atom
  • Alkylamino groups such as 2-amino-ethyl-3-amino-propyl groups, 3-amino-propyl or 1-amino-methyl groups, having a viscosity at 25 0 C of 500-5000 mPas and an amine value of 0.5 to 10.
  • the invention preferably contains the suspension, at least one polymer containing carboxylic acid groups and particulate thickener having the amino groups, wherein the respective group alone or in any mixtures be present together, which bind the polymer physisorptive.
  • the suspension preferably contains particulate thickeners which contain basic groups and polymers which are bonded to particulate thickeners and contain acidic groups.
  • An inventively particularly preferred example of particulate thickeners containing basic groups are here preferably metal oxides, preferably silicic acids, particularly preferably fumed silica which are partially surface-functionalized with aminoalkylsiloxy groups, ie those in which 10 to 90%, preferably 25-75% of the total surface are silylated , preferably those in which 10 to 90%, preferably 25-75%, of the surface silanol groups of the untreated silica are substituted with aminoalkylsiloxy groups.
  • Preferred examples are particulate thickeners, such as, preferably, metal oxides, such as silicic acids, preferably pyrogenic silicas functionalized with aminoalkyl groups, prepared as described in EP-A-896 029, EP-A-1302444, EP-A-1304332, and EP-A- 1473296 described.
  • metal oxides such as silicic acids, preferably pyrogenic silicas functionalized with aminoalkyl groups
  • a preferred example of acidic group-containing polymer according to the invention are preferably polymers which contain acidic carboxyl groups (-COOH) terminally and laterally or only laterally or only terminally, such as polyacrylates, such as polyalkylalkylacrylates, such as polyesters, or weakly acidic hydroxyl groups (-OH).
  • polyacrylates such as polyalkylalkylacrylates, such as polyesters, or weakly acidic hydroxyl groups (-OH).
  • carbinol (-C-OH) groups in alcohols and polyols, such as polyesters, especially those with measurable amounts of free carboxylic acid groups (-COOH) groups, such as those polymers such as for the preparation of 1-component and 2-component polyurethanes for Surfaces- Coatings, adhesives and sealants, glass fiber reinforced plastics are used, in particular those having an acid number according to DIN 53402 or ISO 3682 greater than 1 ml / g, preferably greater than 5 ml / g, more preferably greater than 10 ml / g, most preferably greater than 20 ml / g, more preferably greater than 50 ml / g.
  • suspensions contain greater than 1 percent by weight of carboxyl-containing polymer having an acid number greater than 1 ml / g and greater than 5 weight percent, preferably greater than 10 weight percent, more preferably greater than 15 weight percent and most preferably greater than 18 weight percent of a particulate thickener surface-functionalized with aminoalkylsiloxy groups , such as preferably metal oxides, preferably silica, particularly preferably fumed silica, for example prepared according to EP-A-1304332, with a specific surface area of greater than 150 m 2 / g according to BET.
  • the suspension according to the invention particularly preferably contains 25% by weight and very particularly preferably more than 35% by weight of a fumed silica having a specific surface area of less than 150 m 2 / g according to BET.
  • a preferred example of a suspension according to the invention is preferably polysiloxane, preferably polyalkylsiloxane, more preferably polydimethylsiloxane containing particulate thickener, preferably fumed silica, with polysiloxane, preferably polyalkylsiloxane, especially preferably polydimethylsiloxane grafted.
  • polysiloxane preferably polyalkylsiloxane, more preferably polydimethylsiloxane containing particulate thickener, preferably fumed silica
  • polysiloxane preferably polyalkylsiloxane, especially preferably polydimethylsiloxane grafted.
  • This is preferably done by Aufpolykondensieren or grafting of polydimethylsiloxane on pyrogenic KIESELS ⁇ URE, this can be done by basic, for example with amines or ammonia, catalysis. This can be done, for example, by thermal
  • temperatures of greater than 15O 0 C preferably greater than 200 0 C, required at reaction times greater than 5 hours or preferably at temperatures greater than 25O 0 C, more preferably greater than 300 0 C at reaction times of less than 1 hour.
  • a minimum reaction time of reaction time of less than 15 minutes should not fall below and a maximum temperature of greater than 400 0 C, preferably not greater than 35O 0 C should not be exceeded.
  • Another preferred chemical reaction can be achieved oxidatively at temperatures greater than 100 0 C and oxygen content of greater than 1 percent by volume; a favorable for process reasons preferred variant is the mechano-chemically induced reaction at temperatures greater than -4O 0 C and average shear rates greater than 1000 s "1 and local shear rates greater than 10000 s " 1 .
  • This can be done by suspending and dispersing the silicic acid with high shear aggregates which introduce globally and locally very high shear energies into the suspension, such as mixing turbines, such as high speed kneaders or rolls such as 2 rolls, preferably with a friction greater than 1.01 or so 3-roll.
  • Suspensions exhibiting a fluidity and a soft mass, at a degree of filling of the suspension of up to 50 weight percent of particulate thickener.
  • the particulate thickener preferably fumed silica, a content of polydimethylsiloxane of greater than 10, preferably greater than 25, more preferably greater than 33, more preferably greater than 50 weight percent, measured over the carbon content of greater than 3.3, preferably greater than 8, more preferably greater 11, more preferably larger 50 weight percent.
  • This can preferably be determined for the purpose of analysis by extraction / dissolution and sedimentation with decanting or dissolving and separating centrifuging, and then measuring the isolated particulate thickener, preferably pyrogenic silica on carbon content, for example by elemental analysis.
  • Coating material, adhesive and sealant may preferably be produced, at least using the suspension according to the invention.
  • synthetic or natural rubber or rubber at least using the suspension according to the invention can be prepared.
  • Suspensions according to the invention can be used for the preparation of preferably coating materials, preferably for scratch-resistant coating materials and coating materials with improved surface mechanics, for the production of adhesives and sealants, preferably for high-strength and impact-resistant adhesives and sealants.
  • particulate thickeners such as precipitated silica and fumed silica, pyrogenic
  • Suspensions according to the invention can be used preferably for the preparation of coating materials, adhesives and sealants with a high loading of particulate matter Thickener at the same time low viscosity and thus excellent processability can be used.
  • the suspensions according to the invention can preferably be used for the preparation of peroxide crosslinked or addition-crosslinked silicone rubbers of high degree of filling with pyrogenic silica and high strength, high modulus, high notch strength and high elasticity of the crosslinked compositions while excellent processing properties such as flowability of the uncrosslinked compositions.
  • the suspensions according to the invention can preferably be used to produce high-strength and / or elastic coatings, epoxy-based adhesives and sealants, with high strength, high modulus, high energy fracture and high impact strength, using epoxies as binders and using Jeffamines, polymeric amines, aliphatic Amines and aromatic amines as a hardener, are used.
  • the suspensions according to the invention can preferably be used for producing high-hardness and / or elastic surface coatings from 2-component POLYURETHANES, using polyols as binders and isocyanates as hardeners, wherein surface coatings with high gloss, low surface abrasion and high transparency coupled with excellent scratch resistance with gloss losses less than 50% and high chemical resistance.
  • example 1 2-component POLYURETHANES, using polyols as binders and isocyanates as hardeners, wherein surface coatings with high gloss, low surface abrasion and high transparency coupled with excellent scratch resistance with gloss losses less than 50% and high chemical resistance.
  • hydrophilic fumed silica having a BET specific surface area of 50 m 2 / g, obtainable from Wacker-Chemie GmbH, D, under the name HDK® D05 are added in portions while stirring with a dissolver. Subsequently, this approach is pulped by a bead mill to a grindometer value at the resolution limit of the grindometer test of about 0 to 5 microns. The content of fumed silica is 13.4 percent by weight based on the solids.
  • Example 2 The procedure is as in Example 1, but instead of hydrophilic fumed silica having a BET specific surface area of 50 m 2 / g, available from Wacker-Chemie GmbH, D under the name HDK ® D05 is hydrophilic fumed silica with a BET specific surface area of 150 m 2 / g, available from Wacker-Chemie GmbH, D, under the name HDK® V15.
  • Table 1 Examples 1 to 5 absolute viscosity [mPas].
  • Tinuvin ® 292 a liquid universal light stabilizer (HALS: hindered amine light stabilizer)
  • HALS hinder
  • Example 7 From the batch of Example 7 elevators at dry film thicknesses of 35 .mu.m mounted on glass with the doctor, after storage and drying for 30 minutes at room temperature and cured by storage and curing for 30 minutes at a temperature of 130 0 C in a convection oven. After subsequent storage for 24 hours at room temperature, these films are measured according to ASTM D1003 in transmission.
  • the high clarity of the paint body shows the good and homogeneous colloidal distribution of fumed silica. It will measure an excellent glossy lacquer surface that confirms the excellent low viscosity and leveling properties of the clearcoat.
  • the scratch resistance of the paint surface of the cured paint film according to Example 8 is determined using a Scheuer test device according to Peter-Dahn.
  • a scouring fleece Scotch Brite® 2297 / scouring agent 3M Scotch-Brite CF-HP S-SFN (soft) with an area of 45 x 45 mm with a weight of 1000 g is weighted.
  • the paint samples are scratched with a total of 40 strokes.
  • the gloss of the coating is measured with a gloss meter Microgloss 20 ° from Byk.
  • the loss of gloss compared to the initial value is determined
  • piperidinyl sebacates a mixture of 75% by weight of bis-1,2,3,6,6 Pentamethyl-4-piperidinyl sebacate and 25 weight percent methyl-1,2,2, 6, 6-pentamethyl-4-piperidinyl sebacate
  • Ciba Specialty Chemicals CH under the trade name Tinuvin ® 292 (a liquid universal light stabilizer (HALS: hindered amine light stabilizer)), and 1.0 g of 1 percent
  • Dizinndibutyldilaurat solution in 98 percent butyl acetate, and 0.7 g of a nonionic surfactant based on polyethylene oxide-modified polydimethylsiloxane with a density of 1.04 kg / 1, available under the trade name BYK ® 331 available from Byk-Chemie, D, as a 10 percent solution in 98 percent butyl acetate, and with 10.1 g of the hydroxyl group-containing acrylate resin described above and with 3.0 g of a solvent mixture of SolvessolOO to 98 percent butyl acetate 70 to 30 completed.
  • This total batch of the binder component is 100 to 18.5 with a polyisocyanate of the type HDI trimer as a hardener, with a molecular weight of 505 g / mol, an NCO content of 22% based on solids, with a solids content of 100 percent by weight and a viscosity of 2000 mPas mixed.
  • Example 10 absolute viscosity [mPas] viscous: absolute viscosity at 25 0 CD: shear rate in [l / s]
  • the scratch resistance of the paint surface of the cured paint film according to Example 11 is determined using a Scheuer test device according to Peter-Dahn.
  • a scouring fleece Scotch Brite® 2297 / scouring agent 3M Scotch-Brite CF-HP S-SFN (soft) with an area of 45 x 45 mm with a weight of 1000 g is weighted.
  • the paint samples are scratched with a total of 40 strokes.
  • the gloss of the coating is measured with a gloss meter Microgloss 20 ° from Byk.
  • the loss of gloss compared to the initial value is determined
  • Wacker-Chemie GmbH, D which has a content of aminopropyldimethylsiloxy groups of 0.09 mol / g and for example, in accordance to EP-a-1304332 can be prepared, and has a carbon content of 5 weight percent and a nitrogen content of 1 weight percent, both determined by elemental analysis, (based on a hydrophilic fumed silica having a specific surface area of 300 m 2 / g HDK available from Wacker-Chemie GmbH D, under the trade name HDK® T30), incorporated, incorporated and dispersed with a dissolver Turbotest 33 / 300P, Rayneri.
  • the silica is metered into the liquid phase gradually, first with a number of revolutions of the mixer of 500 revolutions per minute, then for a few minutes at a higher number of revolutions of 3300 per minute, ie about a peripheral
  • Circulation speed of the disc of 11 m / s dispersed before further silica is added When all the silica is incorporated and dispersed, it is dispersed at one revolution to 3300 per minute for 1 hour.
  • By dispersing the fumed silica of the composition may come to 60 and 8O 0 C to heating up.
  • the dispersing quality is monitored with a grindometer to a value close to 0 ⁇ m, with optical microscopy, and with viscosity measurements.
  • the mixture is then finally degassed in a vacuum reactor, for 30 minutes and at one hour at a temperature of 8O 0 C, with slow stirring.
  • the silicic acid contained in the suspension is dissolved by dissolving 2.5 g of the epoxy resin-and-silica suspension according to Example 13, 14 and 15 in 50 ml of tetrahydrofuran and then centrifuging in a laboratory centrifuge at 5000 Separated revolutions per minute and the sediment was washed by taking up five times in tetrahydrofuran and centrifuging free, unbound epoxy resin, cleaned and separated from the unbound epoxy resin, dried and analyzed.
  • This so isolated from the suspension silica has a carbon content of 41 weight percent, as well as a mass loss in the thermogravimetry to 55O 0 C under air of 42 weight percent.
  • the silica is gradually added to the liquid phase, first with a number of revolutions of the mixer of 500 revolutions per minute, then for a few minutes at a higher number of revolutions of 3300 per minute, ie about a peripheral peripheral speed of the disc of 11 m / s dispersed before adding more silica.
  • a number of revolutions of the mixer 500 revolutions per minute
  • a higher number of revolutions of 3300 per minute ie about a peripheral peripheral speed of the disc of 11 m / s dispersed before adding more silica.
  • RPM dispersed at 3300 per minute for 1 hour By dispersing the fumed silica of the composition may come to 60 and 8O 0 C to heating up. The dispersing quality is monitored with a grindometer to a value close to 0 ⁇ m, with optical microscopy, and with viscosity measurements. The mixture is then finally degassed in a vacuum reactor, for 30 minutes and at one hour at a temperature of 8O 0 C, with slow stirring.
  • Example 17 The silicic acid contained in the suspension is separated by dissolving 2.5 g of the epoxy resin and silica suspension according to Example 16 and 17 in 50 ml of tetrahydrofuran and subsequent centrifuging in a laboratory centrifuge at 5000 revolutions per minute and the sediment by five times
  • MDEA Diethylaniline
  • Mn 310 g / mol
  • MDEA Diethylaniline
  • the ratio of DGEBA to MDEA is 71.17 to 28.83.
  • the crosslinking is implemented in a programmable oven: 4 hours at 135 0 C, followed by aftercrosslinking for 4 hours at 19O 0 C.
  • crosslinked masses with fumed silica HDK ® H30RA show a significantly increased strength and impact resistance compared to compositions without fumed silica.
  • Example 16, 17 are crosslinked with DGEBA Dow DER330.
  • DGEBA is heated to 50 0 C, then liquefied and mixed in the compositions from examples 16 and 17, and the mixture placed into a mold.
  • the ratio of DGEBA Dow DER330 to Jeffamine D2000 ® is hereby 27.67 to 72.33.
  • the crosslinking is implemented in a programmable oven: 4 hours at 120 0 C, followed by a post-crosslinking for 4 hours at 15O 0 C.
  • crosslinked masses with fumed silica HDK ® T30 show a significantly increased strength and elasticity compared to compositions without fumed silica.
  • Wacker one aminoalkyl-modified fumed silica available under the trade name HDK ® H30RA from Wacker-Chemie GmbH, D, which has a content of aminopropyldimethylsiloxy groups of 0.09
  • Mol / g and can be prepared, for example, according to EP-A-1304332, having a carbon content of 5% by weight and a nitrogen content of 1% by weight, both determined by elemental analysis (based on a hydrophilic fumed silica having a specific gravity)
  • the silicic acid contained in the suspension is separated by dissolving 2.5 g of the epoxy resin-and-silica suspension in 50 ml of tetrahydrofuran and then centrifuging in a laboratory centrifuge at 5000 revolutions per minute and the sediment by taking up in tetrahydrofuran five times and centrifuging free , unbound epoxy resin, cleaned and separated from the unbound epoxy resin, dried and analyzed.
  • This so isolated from the suspension silica has a carbon content of 41 weight percent, as well as a mass loss in the thermogravimetry to 55O 0 C under air of 42 weight percent. This corresponds to an average reaction of 1.7 moles of amino-hydrogen groups of the Silica HDK ® H30RA with one mole of the epoxy groups of the epoxy resin.

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Abstract

L'invention concerne une suspension qui contient au moins 3 % en poids d'un agent épaississant particulaire, une quantité d'au moins 5 % en poids d'au moins un polymère, par rapport à la masse de l'agent épaississant particulaire pur sans polymère, étant liée à cet agent épaississant particulaire dans la suspension. Eventuellement au moins un autre polymère ou plusieurs polymères sont présents librement dans la suspension. La viscosité relative θ/θ0, les valeurs θ et θ0 étant mesurées à une température identique et à une température de 25 °C, est inférieure à 100 et cette viscosité relative θ/θ0 varie d'un écart inférieur au facteur 10 en cas de stockage pendant au moins une semaine à une température de 40 °C. La suspension selon l'invention comprend une phase liquide qui contient, par rapport à la totalité de la phase liquide, 0 à 80 % en poids d'un solvant ou d'un composant réticulable à faible poids moléculaire présentant une viscosité inférieure à 100 mPas à 25 °C, ainsi que 10 à 100 % en poids d'un composant polymère ou d'un mélange d'au moins deux polymères pouvant être réticulés physiquement ou chimiquement.
EP06764044A 2005-07-28 2006-07-04 Suspensions de hdk stabilisees destinees a renforcer des resines reactives Withdrawn EP1910462A2 (fr)

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DE102005035442A DE102005035442A1 (de) 2005-07-28 2005-07-28 Stabilisierte HDK-Suspensionen zur Verstärkung von Reaktivharzen
PCT/EP2006/063842 WO2007012547A2 (fr) 2005-07-28 2006-07-04 Suspensions de hdk stabilisees destinees a renforcer des resines reactives

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US8071666B2 (en) 2011-12-06
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KR20080039953A (ko) 2008-05-07
CN101233182B (zh) 2011-02-16
DE102005035442A1 (de) 2007-05-16
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