EP2100912B1 - Utilisation de polymères destinés à la modification du chargement de surface de petits éléments solides - Google Patents

Utilisation de polymères destinés à la modification du chargement de surface de petits éléments solides Download PDF

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EP2100912B1
EP2100912B1 EP08004248A EP08004248A EP2100912B1 EP 2100912 B1 EP2100912 B1 EP 2100912B1 EP 08004248 A EP08004248 A EP 08004248A EP 08004248 A EP08004248 A EP 08004248A EP 2100912 B1 EP2100912 B1 EP 2100912B1
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Prior art keywords
polymer
particles
acid
monomers
monomer
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EP2100912A1 (fr
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Manfred Weuthen
Sabine Both
Frederic Bauer
Rüdiger Dr. Hartung
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Cognis IP Management GmbH
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Cognis IP Management GmbH
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Priority to ES08004248T priority Critical patent/ES2363107T3/es
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Priority to AT08004248T priority patent/ATE507259T1/de
Priority to DE502008003350T priority patent/DE502008003350D1/de
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1655—Process features
    • C23C18/1662—Use of incorporated material in the solution or dispersion, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
    • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials

Definitions

  • the present invention relates to the change in the surface charge of solid particles measured on their zeta potential, and the use of such modified particles for the preparation of stable suspensions, for example in galvanic processes and as additives in lubricant compositions, in organic solvents, in polymeric materials, as flotation or as Auxiliary in aqueous slurries of clay minerals or in cosmetic or pharmaceutical compositions.
  • solid particles which are dispersed in liquid, preferably aqueous media.
  • liquid preferably aqueous media.
  • dyes which contain dispersed pigments, but also dispersed fillers in polymers or dispersions in the field of pharmaceuticals, cosmetics or detergents and cleaners are known.
  • clay dispersions the so-called slip
  • flotation for example of ores also dispersions are used.
  • a further technical example of dispersions occurs in the galvanization of metal surfaces (or according prepare other surfaces):
  • boron nitride (BN) is used in the galvanic nickel plating of metal surfaces in dispersed form in the galvanic bath, as the BN then together with the nickel the metal surface precipitates and improves the physical properties of the nickel layer.
  • Dispersions are systems of several phases, one of which is dispersed continuously (dispersing agent ) and at least one more (dispersed phase, dispersant ).
  • Examples of dispersions are emulsions (liquid phases insoluble in one another), aerosols or the suspensions in question in the form of dispersed solid, preferably non-metallic, inorganic particles in a liquid phase.
  • a molar dispersion is the molar-disperse distribution of one substance in another, ie here is a real solution.
  • the energy for producing a dispersion can be supplied, for example, chemically, electrochemically, electrically or mechanically (by grinding, by means of ultrasound, etc.).
  • dispersions are prone to phase separation (sedimentation), so that stabilization with emulsifiers or protective colloids is carried out during their preparation and storage.
  • the electrostatic repulsion in the same direction charged pigment or polymer particles is also exploited (electrostatic stabilization).
  • water-soluble polymers are suitable for improving the dispersing properties of solid particles, preferably inorganic particles, in liquid, preferably in aqueous media.
  • the polymers are known compounds known in the art EP 1 767 554 A1 the applicant are described, wherein in the document, a manufacturing method for these polymers is disclosed.
  • the weight fraction of monomers c) is less than 15 wt.% And in particular equal to or less than 10 wt .-%.
  • a preferred weight range for the monomer c) is 5 to 25, preferably 5 to 15 and in particular from 5 to 10 wt .-%, each based on the total weight of the polymer.
  • the polymers of the invention comprise as polymerized monomers at least three different monomers a) to d). In this case, all polymers are included which contain either the monomer units a), b) and c), or a), b) and d) or a), b), c) and d) side by side. It is also within the meaning of the present invention possible to use mixtures of the listed polymers.
  • R 1 is a methyl radical
  • R 2 is a CH 2 -CH 2 -CH 2 group
  • R 3 , R 4 and R 5 are each methyl.
  • X - represents a suitable counterion such as halide, hydroxide, sulfate, hydrogen sulfate, phosphate, formate or acetate, preferably chloride.
  • MATAC 3-trimethylammoniumpropylmethacrylamidchlorid
  • ethylenically unsaturated acids and their salts such as acrylic or methacrylic acid are suitable.
  • Acrylic acid (AA) is the most preferred monomer here.
  • Particularly suitable salts are their alkali metal and ammonium salts.
  • DMAC dimethyldiallylammonium chloride
  • DMAE 2-dimethylaminoethyl (meth) acrylate
  • DMAP 2-diethylaminoethyl (meth) acrylate
  • DMADMPA 3-dimethylamino-2, 2-dimethylpropyl acrylamide
  • the polymers used according to the invention are water-soluble, ie that at least 0.1 g of the polymer in 100 ml of water at 20 ° C are soluble.
  • the polymers are ampholytic, ie the polymers have both acidic and basic hydrophilic groups and behave acidic or basic depending on the condition.
  • the polymers of the invention preferably have a mean molecular weight (weight average molecular weight, M w), measured by gel permeation chromatography aqueous (GPC) with light scattering detection (SEC-MALLS), in the range of 10,000 to 500,000 Da.
  • M w weight average molecular weight
  • SEC-MALLS light scattering detection
  • the molecular weight of the polymers is between 50,000 and 350,000 Da and in particular between 100,000 and 250,000 Da.
  • a particularly preferred range may be between 110,000 and 140,000 Da.
  • the various monomer building blocks a) to d) preferably coexist in certain selected proportions. Preference is given in each case to those polymers which contain the component b) in excess (both based on moles and on Weight of the components) to components a) and c). Preference is given here to polymers in which the molar ratio between the monomers a), b) and c) is in the range from 1: 10: 1 to 5: 10: 5 and preferably in the range from 4: 10: 1 to 4: 10: 3 and especially in the range of 3: 8: 2 to 3: 8: 1.
  • the monomer component of type d) is present, the same conditions apply analogously.
  • particularly preferred polymers may be those which contain both monomers of type c) and of type d) side by side.
  • the monomer units c) and d) are then present in a molar ratio of 2: 1 to 1: 2, more preferably in a ratio of 1: 1, side by side.
  • Particularly preferred polymers with four different monomer building blocks have molar ratios a): b): c): d) of 2: 4: 1: 1 to 1: 10: 1: 1.
  • a particularly preferred ratio is 3: 8: 1: 1.
  • Preferred polymers are in particular those in which the monomer a) is selected from those compounds of the general formula in which R 1 is a methyl group, R 2 is an alkylene radical having 3 C atoms, R 3 , R 4 and R 5 are each methyl radicals and X is chloride, the monomer b) is selected from those compounds of the general formula in which R 6 and R 7 are a hydrogen atom and R 8 is an isopropyl radical and monomer c) is acrylic acid.
  • polymers in which the monomer a) is selected from those compounds of the general formula in which R 1 is a methyl group, R 2 is an alkylene radical having 3 C atoms, R 3 , R 4 and R 5 are each methyl and X is are chloride, the monomer b) is selected from those compounds of the general formula in which R 6 and R 7 are a hydrogen atom and R 8 is an isopropyl radical and monomer c) for H 2 C CR-CO-NH-CR ' R "R"'- SO 3 H and salts thereof, in particular the alkali metal and ammonium salts, where R, R', R "and R '" independently of one another represent a hydrogen atom or an alkyl (ene) radical having 1 to 4C -Atoms stands, is.
  • the monomers a) and b) must necessarily be present in a molar ratio of 1: 1 to 1:10 and in addition the monomers c) and / or d), wherein as monomer a) the 3-trimethylammonium-propylmethacrylamidchlorid (MAPTAC), as monomer b) the N-isopropylacrylamide (NIP AM), as monomer c) acrylic acid (AA) and / or methacrylic acid (MA), as monomer d) 2-acrylamido-2-methyl-1-propanesulfonic acid (AMPS) are selected, with the proviso that in the water-soluble polymer, the monomer c) in amounts of at most 25 wt.% Based on the total weight of the water-soluble polymer is.
  • MA 3-trimethylammonium-propylmethacrylamidchlorid
  • a preferred weight range for the monomer c) is 5 to 25, preferably 5 to 15 and in particular from 5 to 10 wt .-%, each based on the total weight of the polymer.
  • the indices m, n, p and q represent the number of monomer building blocks NIPAM, MAPTAC, AA and AMPS in the polymer molecule.
  • sequence of the building blocks in the polymers according to the invention is generally not necessarily predetermined; rather, all sequences of the individual building blocks, whether blocks of the individual monomers or their purely statistical sequence in the molecule, are encompassed.
  • those derivatives are particularly preferred which contain the monomers MAPTAC, NIPAM and AMPS in weight ratios of from 25 to 50% MAPTAC, 40 to 75% NIPAM and 1 to 15% AMPS polymerized, with the proviso that the percent summer gives 100.
  • An independently preferred polymer is one which contains the monomers MAPTAC, NIPAM and AA polymerized in the weight ratios of 25 to 50% MAPTAC, 40 to 75% NIPAM and 1 to 15% AA, with the proviso that the percentages of the percents are 100 results.
  • a water-soluble polymer at 20 ° C. is also preferred in that it contains the monomers MAPTAC, NIPAM, AA and AMPAS in a weight ratio of 25 to 45% MAPTAC, 40 to 70% NIPAM, 1 to 15% AA and 1 to 15% AMPS contains, provided that the sum of the percentage shares 100.
  • Polymers as described above can be made by polymerization processes known to those skilled in the art. They can be prepared, for example, by solution polymerization or bulk polymerization. Preferably, they are prepared by solution polymerization, ie, a polymerization of monomers in solvents and / or water, in which both the monomers and the polymers resulting from them are soluble. Furthermore, the polymerization can be carried out with presentation of the total amount of monomer or with monomer feed, batchwise, semicontinuously or continuously. Preferably, the polymerization is carried out as a batch polymerization with or without monomer feed.
  • the above-described water-soluble polymers have the property of measuring the surface charge of solid particles measured e.g. via their zeta potential of an aqueous dispersion of the particles to reload.
  • the measurement of the zeta potential is a common method for the characterization of solid / liquid dispersions.
  • Dispersed particles can become electrically charged, for example by adsorption of ions on their surface.
  • an electric double layer forms on the surface of these electrically charged particles, which is firmly bound to the particles and causes an apparent volume increase.
  • This solid layer is enveloped by a mobile and diffused ion layer.
  • the potential ⁇ 0 at the particle surface now drops linearly within the solid ion layer with the thickness ⁇ to the value ⁇ ⁇ in order to return approximately exponentially in the diffuse layer to the value 0.
  • the potential difference between the inner solid ion layer ⁇ ⁇ and the Point within the diffused ion layer, where the potential has decreased to 1 / e ⁇ ⁇ ⁇ is called the zeta potential.
  • the migration rate is measured either by light microscopic observation or, in particular in the case of smaller particles, by means of laser correlation spectroscopy.
  • the polymers used according to the invention cause the respective treated particles to undergo a transloading to the surface, for example from a positive to a negative charge value, or vice versa.
  • Preferred are changes from a negative to a positive zeta potential of the particles.
  • An object of the present application relates to solid particles preparable by contacting a carrier particle in an aqueous medium with a polymer as described above.
  • the solid particles in an aqueous medium are contacted with a polymer as described above with the polymer itself in the aqueous solution and the polymer solution mixed with the solid particles.
  • the solid particles are separated from the solution, for example by filtration and the separated particles are then dried.
  • the polymer solution in the treatment of the solid particles is carried out at a temperature of 10 to 90 ° C, preferably 15 to 35 ° C and especially at 18 to 30 ° C.
  • the pH during the process is preferably in the range of ⁇ 1 to 14, preferably between 1 and 14 and can, especially in Galavin baths particularly preferably in the acidic range, in particular in the range of 1 to 5 and advantageously in the range of 1 to 3 lie.
  • the method according to the invention advantageously differs from the prior art, which uses surfactants which are generally no longer stable under such extreme conditions.
  • the particles which are preferably treated with the polymers preferably have a diameter between 10 and 0.00001 mm, with particles with diameters of 1 to 0.0001 mm or 0.1 to 0.001 mm being preferred. Preference is furthermore given to those particles in which an aqueous solution of the polymer is used which has a weight fraction of polymer of from 0.01 to 30% by weight, preferably from 0.1 to 15 and in particular from 1 to 10% by weight , in each case based on the total weight of the aqueous solution.
  • the particles are preferably non-metallic, inorganic particles.
  • the solid particles thus translocated on the surface which are also the subject of the present invention, and the aqueous dispersions of such particles can preferably be used in galvanic processes (electrolytic or chemical) or as additives in lubricant compositions, or in organic solvents or in polymeric materials.
  • galvanic processes electrolytic or chemical
  • additives in lubricant compositions, or in organic solvents or in polymeric materials.
  • such particles according to the invention can also be used as flotation auxiliaries or as aids for the slurry of clay minerals.
  • Electroplating is generally understood to mean the electrochemical surface treatment of materials, ie the electrolytic deposition of metallic (or even non-metallic) thin layers for the purpose of beautification, protection against corrosion, the production of composite materials with improved properties and the like. Electroplating encompasses the two main areas of galvanostasis and electroforming. Electroforming is used to manufacture or reproduce articles by electrolytic deposition. For this purpose, the original form first an impression (negative, mold) of gypsum, wax, gutta-percha, silicone rubber, low-melting metal alloys, etc. produced.
  • the casting is rendered superficially electrically conductive (by chemical precipitation or vapor deposition of metals) and then coated as a negative pole in the plating liquid with the metal to be deposited (eg Cu, Ni, Ag, etc., plus pole).
  • the metal to be deposited eg Cu, Ni, Ag, etc., plus pole.
  • the metal layer formed can be lifted off the mold u. if necessary pour out with filler for reinforcement.
  • Galvanostegie a method of coating objects with mostly very thin, protective and beautifying coatings of compliment, gold, nickel, chromium, copper and the like on less valuable documents (eg iron) with the help of electric current. Examples are silvering, gilding, chrome plating, etc. It is between electroless, ie with chem. Reducing agents working methods and electrolytic processes (“electroplating") distinguished.
  • the article to be plated is electrically nonconductive, it must be made conductive.
  • the metallization of the article can also be done in vacuum (ion plating) or melting. It is also known that surface cavities of electrically non-conductive materials are provided with nucleating agents, for example palladium chloride.
  • Galvanization in the broadest sense also includes preparatory processes, such as chemical and electrolytic degreasing, pickling, polishing (in particular so-called electropolishing) and dyeing, and in particular the chemical deposition of metal and oxide layers.
  • the workpieces to be plated must be thoroughly cleaned before being introduced into the plating bath and treated with the means of metal degreasing.
  • the galvanic baths are divided into acidic and alkaline baths.
  • the acid baths contain sulfates, chlorides, fluoroborates and sulfamates of the metals to be deposited, while the alkaline baths are based on hydroxo- or cyano complexes or diphosphates.
  • gloss galvanization is obtained as a result of using certain additives that have a leveling effect (brighteners), immediately a shiny galvanic coating, the subsequent polishing often redundant.
  • the workup of spent galvanizing u. the removal of surfactant, metal, salt and acid residues from the Wastewater not only serves to recover valuable raw materials (recycling), but also to clean water and thus protect the environment.
  • a further subject of the application is therefore directed to a preferably surfactant-free process for galvanic or autocatalytic metal deposition on metallic surfaces, for example for the nickel plating of metallic surfaces, which comprises adding to an aqueous nickel solution containing at least one Ni salt, an organic acid and a inorganic phosphorus compound is an aqueous dispersion of boron nitride particles (preferably hexagonal BN) prepared as described above and then contacting this solution with the metallic surface until a metal-boron nitride particle dispersion layer has been deposited thereon ,
  • boron nitride particles preferably hexagonal BN
  • the solid particles for the purposes of the present invention are to be used as additives in lubricant compositions, in organic solvents, in pharmaceutical preparations, in cosmetic compositions or as flotation auxiliaries. Furthermore, such particles may find application in the matrix of polymeric materials (duroplastic or thermoplastic polymers), preferably dispersed fillers in polymers, or they may find utility as an aid to the aqueous slurry of clay minerals.
  • the latter enters the production of the so-called slip, which is used to produce ceramic materials, preferably porcelain.
  • Flotation is known to be a separation process for the treatment of ores, coal, salts or wastewaters.
  • the flotation makes the different interfacial tension of solids to liquids (mostly water) and gases (mostly air) - i. the different wetting in the water of suspended particles - use; Phenomena of adhesion, zeta potential and, in general, electrochemical double layer play a role at the interfaces.
  • metal sulfides many metal oxides, heavy metals, carbon and diamond are readily wetted by water repellent (hydrophobic) species such as aliphatic or aromatic hydrocarbons, gait (dead rock), namely quartz, silicates, phosphates, sulfates, carbonates, halides and the like. Like. However, slightly of water u. hydrophilic substances.
  • the flotation is based on the fact that wetted particles sink, but not wetted - with a grain size between 10 and 500 microns - to accumulate on the suspension (turbid) led air bubbles, to the surface migrate (creaming) and can be removed together with the foam ,
  • the wettability of the substances to be separated can be selectively influenced by the addition of flotation auxiliaries. These are chemicals that improve the wettability of various mineral surfaces. This function can also be used according to the invention polymers according to the above Description exercise. Solid, wetted with the polymers particles are suitable to improve flotation, for example, by facilitating the separation of the solids from the aqueous phase, and thus increase, for example, the yield of floated materials.
  • a terpolymer according to the invention was prepared as follows: 12.4 g of MAPTAC, 1.4 g of acrylic acid and 50 g of water were mixed. The pH of the aqueous mixture was adjusted in the range of 6.5 to 7.5. Then, 8.5 g of NIPAM and 23 g of isopropanol were added, and this mixture was heated to 65 ° C. Then, as a starter, 0.15 g of 2,2'-azobis (2-amidinopropane) dihydrochloride was added and the reaction started. The mixture is heated to about 80 ° C. After the reaction had elapsed, the azeotrope water / isopropanol was distilled off at 80-100 ° C. The concentration of the resulting polymer solution was about 22 wt .-%. The pH of the solution was 5 to 7.5. The polymer had a molecular weight of 130,000 Da (measured by SEC-MALLS).
  • Specimens of boronitride, silicon carbide, and boron carbide powders were tested: To this was added an aqueous solution containing 5% by weight of a polymer according to the synthesis under "1.” produced. Each 1.0 g of the powder samples were suspended in each 99.0 g of the aqueous polymer solution and stirred for 72 hours. Subsequently, the suspension was filtered off. The residue was washed with water and dried at 80 ° C for 12 hours. The dry residue was subsequently suspended in 100 ml of water.
  • the treated samples agglomerated only very weakly in the aqueous suspension.
  • Exemplary is in illustration 1 this effect is shown photographically for a boron nitride powder with a particle diameter of 0.5 ⁇ m.
  • the polymer-treated boron nitride powder is much more stable in levitation than the untreated boron nitride powder.
  • the zeta potential of the aqueous suspensions of boron nitride, silicon carbide, and boron carbide powders was determined (see Figure 2 ). The measurement was carried out with a Coulter DELSA 440 SX measuring device. It can be seen that the untreated particles have a negative surface charge, whereas the particles treated according to the invention have been reloaded and have a positive charge. A transhipment of the original surface charge has succeeded.
  • the polymer-treated boron nitride from Example 1 was used in a chemical galvanization.
  • the chemical Ni electrolyte was used to study, composed of: nickel sulfate, acetic acid, sodium hypophosphite monohydrate and a stabilizer (commercial product. SurTech ® 835).
  • 10 g of treated boron nitride were used per liter of nickel bath. Scanning electron micrographs show that there is no boron nitride in the deposited nickel layer without treatment ( Figure 3 ).
  • Boron nitride pretreated with the polymer contains about 10- 20% BN ( Figure 4 ).

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Claims (20)

  1. Utilisation d'un polymère, au moins 0,1 g du polymère étant soluble dans 100 ml d'eau à 20°C, et de tels polymères contenant sous forme de motifs polymérisés au moins un de chacun des monomères
    a) H2C=CR1-CO-NH-R2-N+R3R4R5X-
    R1 représentant un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone, R2 représentant un radical alkylène linéaire ou ramifié ayant de 1 à 12 atomes de carbone et R3, R4, R5 représentant chacun indépendamment un atome d'hydrogène, un radical alkyle ayant de 1 à 18 atomes de carbone ou un radical phényle, et X- représentant un anion choisi dans le groupe des halogènes, sulfates ou alkylsulfates, ou représentant un hydroxyde, phosphate, acétate, formiate ou ammonium, et
    b) H2C=CR6-CO-NR7R8
    R6 représentant un atome d'hydrogène ou un radical alkyle ayant de 1 à 4 atomes de carbone et R7 et R8 représentent chacun, indépendamment l'un de l'autre, un atome d'hydrogène, un radical alkyle ayant de 1 à 4 atomes de carbone ou un radical cycloalkyle en C3-C6, étant entendu que R7 et R8 ne représentent pas simultanément un atome d'hydrogène, et
    c) acide acrylique et/ou acide méthacrylique et/ou
    d) d'autres monomères choisis dans le groupe des acides carboxyliques en C3-C6 à insaturation monoéthylénique, tels que l'acide crotonique, l'acide maléique, l'anhydride maléique, l'acide fumarique, l'acide itaconique, ainsi que leurs hémiesters, et sels ou H2C=CR-CO-NH-CR'R"R"'-SO3H ainsi que leurs sels, en particulier les sels de métaux alcalins et d'ammonium, R, R', R'' et R''' représentant, indépendamment les uns des autres, un atome d'hydrogène ou un radical alkyl(èn)e ayant de 1 à 4 atomes de carbone,
    étant entendu que dans le polymère le monomère c) est contenu en quantités d'au maximum 25 % en poids par rapport au polymère, pour la dispersion de particules solides dans des milieux liquides, de préférence aqueux.
  2. Utilisation selon la revendication 1, caractérisée en ce qu'on utilise un polymère soluble dans l'eau à 20 °C, contenant au moins trois monomères différents a), b), c) et/ou d), étant entendu que les monomères a) et b) doivent obligatoirement être contenus en un rapport molaire de 1 : 1 à 1 : 10 et qu'en outre les monomères c) et/ou d) sont contenus, en choisissant
    comme monomère a) le chlorure de 3-méthacrylamido-propyltriméthylammonium (MAPTAC),
    comme monomère b) le N-isopropylacrylamide (NIPAM),
    comme monomère c) l'acide acrylique (AA) et/ou l'acide méthacrylique (MA),
    comme monomère d) l'acide 2-acrylamido-2-méthyl-1-propanesulfonique (AMPS)
    étant entendu que dans le polymère hydrosoluble le monomère c) est contenu en quantités d'au maximum 25 % en poids, par rapport au poids total du polymère hydrosoluble.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que dans le polymère les monomères MAPTAC, NIPAM et AMPS sont contenus polymérisés en des rapports pondéraux de 25 à 50 % de MAPTAC, 40 à 75 % de NIPAM et 1 à 15 % d'AMPS, étant entendu que la somme des proportions en pourcentage est égale à 100 %.
  4. Utilisation selon au moins l'une des revendications 1 à 3, caractérisée en ce que dans le polymère les monomères MAPTAC, NIPAM et AA sont contenus polymérisés en des rapports pondéraux de 25 à 50 % de MAPTAC, 40 à 75 % de NIPAM et 1 à 15 % d'AA, étant entendu que la somme des proportions en pourcentage est égale à 100 %.
  5. Utilisation selon au moins l'une des revendications 1 à 4, caractérisée en ce que dans le polymère les monomères MAPTAC, NIPAM, AA et AMPS sont contenus en des rapports pondéraux de 25 à 45 % de MAPTAC, 40 à 70 % de NIPAM, 1 à 15 % d'AA et 1 à 15 % d'AMPS, étant entendu que la somme des proportions en pourcentage est égale à 100 %.
  6. Utilisation selon au moins l'une des revendications 1 à 5, caractérisée en ce que dans le polymère le rapport molaire entre les monomères a), b) et c) ou d) se situe dans la plage de 1 : 10 : 1 à 5 : 10 : 5 et de préférence dans la plage de 4 : 10 : 1 à 4 : 10 : 3 et en particulier dans la plage de 3 : 8 : 2 à 3 : 8 : 1.
  7. Utilisation selon au moins l'une des revendications 1 à 6, caractérisée en ce que dans le polymère le rapport molaire entre les monomères a), b), c) et d) est de 3 : 8 : 1 : 1.
  8. Utilisation selon au moins l'une des revendications 1 à 7, caractérisée en ce que dans le polymère sont contenus 20 à 30 % en poids de monomère a), 50 à 70 % en poids de monomère b) et 10 à 20 % en poids de monomère(s) c) et/ou d), étant entendu que la somme des proportions est égale à 100.
  9. Utilisation selon au moins l'une des revendications 1 à 8, caractérisée en ce que dans le polymère les monomères c) et d) sont présents en un rapport pondéral entre eux de 1 : 1.
  10. Utilisation selon au moins l'une des revendications 1 à 9, caractérisée en ce que les polymères présentent une masse moléculaire moyenne dans la plage de 10 000 à 500 000 Da, de préférence de 50 000 Da à 350 000 Da et en particulier de 100 000 à 250 000 Da.
  11. Utilisation selon au moins l'une des revendications 1 à 10, caractérisée en ce que les particules sont choisies parmi des composés organiques, de préférence dans le groupe des oxydes, hydroxydes, carbures, borures, sulfures ou nitrures.
  12. Utilisation selon au moins l'une des revendications 1 à 11, caractérisée en ce que les particules solides sont choisies dans le groupe constitué par le nitrure de bore (BN), le carbure de silicium, (SiC), ou le carbure de bore (B4C).
  13. Utilisation selon au moins l'une des revendications 1 à 12, caractérisée en ce que les particules solides présentent des diamètres compris entre 10 et 0,00001 mm.
  14. Particules solides, pouvant être produites par mise en contact d'une particule de support, dans un milieu aqueux, avec un polymère selon la description de la revendication 1, le polymère se trouvant dans une solution aqueuse, et après le traitement séparation et séchage des particules solides ou maintien direct de ces particules dans la solution.
  15. Particules selon la revendication 14, caractérisées en ce que pour la production on utilise une solution aqueuse du polymère qui présente une teneur pondérale en polymère de 0,01 à 30 % en poids, de préférence de 0,1 à 15 et en particulier de 1 à 10 % en poids, chaque fois par rapport au poids total de la solution aqueuse.
  16. Particules selon au moins une des revendications 14 et 15, caractérisées en ce que dans la préparation on effectue l'étape de la mise en contact des particules avec la solution de polymère à des températures de 10 à 90 °C, de préférence de 15 à 35 °C et en particulier de 18 à 30 °C.
  17. Particules selon au moins une des revendications 14 à 16, caractérisées en ce que dans la production on disperse les particules solides dans la solution de polymère.
  18. Utilisation de particules solides, produites selon la revendication 14, dans des procédés galvanoplastiques (par voie électrolytique ou chimique) ou en tant qu'additif dans des compositions de lubrifiants, dans des solvants organiques, dans des matériaux polymères, ou en tant qu'adjuvant de flottation ou en tant qu'adjuvant dans la mise en suspension de minéraux argileux.
  19. Utilisation selon la revendication 18, caractérisée en ce qu'on utilise en tant que particules solides du nitrure de bore.
  20. Procédé pour le dépôt galvanoplastique ou autocatalytique de métaux sur des surfaces métalliques, par exemple pour le nickelage de surfaces métalliques, caractérisé en ce qu'à une solution aqueuse de nickel, contenant au moins un sel de Ni, un acide organique et un composé phosphoré inorganique, on ajoute une dispersion aqueuse de particules de nitrure de bore, qui ont été produites selon la revendication 14, et on met ensuite cette solution en contact avec la surface métallique, jusqu'à ce qu'une couche de dispersion, à base de métal et de particules de nitrure de bore, se soit déposée sur celle-ci.
EP08004248A 2008-03-07 2008-03-07 Utilisation de polymères destinés à la modification du chargement de surface de petits éléments solides Active EP2100912B1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
ES08004248T ES2363107T3 (es) 2008-03-07 2008-03-07 Empleo de polímeros para la modificación de la carga superficial de partículas sólidas.
EP08004248A EP2100912B1 (fr) 2008-03-07 2008-03-07 Utilisation de polymères destinés à la modification du chargement de surface de petits éléments solides
AT08004248T ATE507259T1 (de) 2008-03-07 2008-03-07 Verwendung von polymeren zur modifizierung der oberflächenladung fester teilchen
DE502008003350T DE502008003350D1 (de) 2008-03-07 2008-03-07 Verwendung von Polymeren zur Modifizierung der Oberflächenladung fester Teilchen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP08004248A EP2100912B1 (fr) 2008-03-07 2008-03-07 Utilisation de polymères destinés à la modification du chargement de surface de petits éléments solides

Publications (2)

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EP2100912A1 EP2100912A1 (fr) 2009-09-16
EP2100912B1 true EP2100912B1 (fr) 2011-04-27

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JP2017538860A (ja) * 2014-10-24 2017-12-28 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 固体粒子の表面荷電を改変するための、非両性の四級化可能な水溶性ポリマー
WO2016062879A1 (fr) * 2014-10-24 2016-04-28 Basf Se Éléments de meulage et procédé de production d'éléments de meulage

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Publication number Priority date Publication date Assignee Title
US145517A (en) 1873-12-16 Improvement in agricultural boilers
CH623851A5 (fr) 1975-10-04 1981-06-30 Akzo Nv
NL176436C (nl) 1975-10-04 1985-04-16 Akzo Nv Werkwijze voor de bereiding van positief geladen, stabiele suspensies van polyfluorkoolstofverbindingen.
JP2534208B2 (ja) * 1988-03-17 1996-09-11 三井サイテック 株式会社 推進工法
US5391359A (en) * 1993-01-29 1995-02-21 Phillips Petroleum Company Water dispersible thickeners comprising hydrophilic polymers coated with particulate fatty acids or the salts thereof
FR2774994B1 (fr) * 1998-02-13 2000-05-05 Rhodia Chimie Sa Particules composites comprenant un coeur a base d'un polymere organique contenant une matiere active et un revetement externe a base d'au moins un oxyde et/ou un hydroxyde, leur procede de preparation et leurs utilisations
WO1999048953A1 (fr) * 1998-03-23 1999-09-30 Nippon Zeon Co., Ltd. Composition de dispersion polymere
FR2804046B1 (fr) * 2000-01-21 2002-07-05 Bio Merieux Procede de preparation de particules colloidales stables fonctionnalisees et particules obtenues
WO2002096954A1 (fr) * 2001-05-28 2002-12-05 Atofina Preparation de poudres de polymeres hydrophiles de faible granulometrie
ES2295590T3 (es) * 2002-05-22 2008-04-16 Basf Construction Polymers Gmbh Utilizacion de polimeros solubles en agua como agentes coadyuvantes de la desecacion para la produccion de agentes dispersantes polimericos.
SE525758C2 (sv) * 2002-08-16 2005-04-19 Perstorp Specialty Chem Ab Vattenburen homo- eller sampolymerdispersion, förfarande för dess framställning samt dess användning i bindemedel för dess framställning samt dess användning i bindemedel för ytbeläggningar
SE526998C2 (sv) * 2003-07-01 2005-12-06 Celanese Emulsions Norden Ab Förfarande för framställning av en vattenburen sampolymerdispersion, samt användning därav
US7807766B2 (en) 2005-09-21 2010-10-05 Cognis Ip Management Gmbh Polymers for use in cleaning compositions

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DE502008003350D1 (de) 2011-06-09
ATE507259T1 (de) 2011-05-15
EP2100912A1 (fr) 2009-09-16
ES2363107T3 (es) 2011-07-20

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